EP0697415B1 - Cyclodextrin derivatives with at least one nitrogen containing heterocycle, their preparation and use - Google Patents

Description

The invention relates to cyclodextrin derivatives at least one nitrogen-containing heterocycle, their Manufacture and use.

There are already a number of reactive cyclodextrin derivatives as well as processes for their preparation. So describes EP-A-483380 from Toppan Printing Method for the production of cyclodextrin-containing polymers the aldehyde groups in protected or unprotected form be introduced into the cyclodextrin, which then with the react nucleophilic hydroxyl groups of a polymer. The Binding of cyclodextrins to polymers via an acetal bond, as described in patent application EP-A-483380, is due to the known lability of acetals under acidic Conditions not advantageous.

A. Deratani and B. Pöpping (Makromol. Chem., Rapid Commun. 13, 237-41 (1992)) describe the preparation of a cyclodextrin-chlorohydrin (3-chloro-2-hydroxypropyl-cyclodextrin derivative) by reacting β-cyclodextrin in the aqueous medium with epichlorohydrin under Lewis acidic conditions with Zn (BF ₄ ) ₂ as catalyst. Under basic conditions, this derivative is able to react with nucleophiles such as OH ^- ions (sodium hydroxide solution). Disadvantageously, only a very slight incorporation of epichlorohydrin was achieved in the reaction of cyclodextrin with epichlorohydrin under Lewis acidic conditions. It was therefore necessary to work with a very high excess of epichlorohydrin, which inevitably leads to a large amount of extremely toxic or carcinogenic by-products which have to be separated off and destroyed.

The invention relates to cyclodextrin derivatives, the
characterized in that they contain at least one nitrogen-containing heterocycle with at least one electrophilic center, wherein
the electrophilic centers are the same or different and are carbon atoms to which halogen, in particular F, Cl, or an ammonium substituent, in particular trialkylammonium or a substituted or unsubstituted pyridinium substituent, is covalently bonded.

preferably the nitrogen-containing heterocycle includes up to 3 electrophilic centers.

The substituent distribution of the substituents according to the invention on the cyclodextrin is preferably unselective.

wobei R OH oder OR¹ oder R² bedeutet und

R¹ ein hydrophiler Rest ist, welcher gleich oder verschieden sein kann und

R² ein entweder direkt angeknüpfter oder ein über einen Spacer mittels einer Ether, Thioether, Ester oder Amin-Bindung angeknüpfter stickstoffhaltiger Heterocyclus ist,

wobei der Spacer ein Alkyl bzw. Hydroxyalkylrest mit 1-12 Kohlenstoffatomen ist, der über eine Ether, Thioether, Ester oder Amin-Bindung an die Anhydroglukose gebunden ist und

der stickstoffhaltige Heterocyclus mindestens einen Halogen- oder einen Ammonium-Substituenten umfaßt und mindestens einmal pro Cyclodextrin vorhanden ist und

n 6, 7 oder 8 bedeutet .

The cyclodextrin derivatives of the following formula I are preferably sufficient:

where R is OH or OR ¹ or R ² and

R ^{1 is} a hydrophilic radical which can be the same or different and

R ^{2 is} a nitrogen-containing heterocycle which is either directly attached or is attached via a spacer by means of an ether, thioether, ester or amine bond,

wherein the spacer is an alkyl or hydroxyalkyl radical with 1-12 carbon atoms which is bonded to the anhydroglucose via an ether, thioether, ester or amine bond and

the nitrogen-containing heterocycle comprises at least one halogen or an ammonium substituent and is present at least once per cyclodextrin and

n means 6, 7 or 8.

R ¹ is preferably the same or different and means methyl, ethyl, n- or i-propyl, n- or i-butyl, C ₂ -C ₆ -hydroxyalkyl such as hydroxethyl, hydroxy-i-propyl, hydroxy-n-propyl, C. ₃ -C ₆ oligohydroxyalkyl such as dihydroxy-i-propyl, dihydroxy-n-propyl, C ₁ -C ₄ carboxyalkyl (in the form of the free acid or as alkali salt) such as carboxymethyl, carboxyethyl, carboxy-i-propyl, carboxy- n-propyl or an alkali salt of the carboxyalkyl substituents mentioned, acetyl, propionyl, butyryl, sulfate, C ₁ -C ₄ sulfonic acid alkyl (in the form of the free acid or as alkali salt), C ₂ -C ₄ carboxyhydroxyalkyl (in the form of the free acid or as alkali salt), C ₂ -C ₄ sulfonic acid hydroxyalkyl (in the form of the free acid or as alkali salt) and oxalyl, malonyl, succinyl, glutaryl, adipinyl (in the form of the free acid or as alkali salt).

R³ gleich oder verschieden ist und O,

S, NH, oder NR⁷ bedeutet und

R⁷ gleich oder verschieden ist und C₁-C₆-Alkyl bedeutet und

R⁴ gleich oder verschieden ist und H oder OH bedeutet und

R⁵ NH, NR⁷, S, O, oder

besonders bevorzugt O bedeutet, und

R⁶ für den Fall das R⁵ NH, NR⁷, S, oder O bedeutet entweder

ist,

wobei R⁸ und R⁹ gleich oder verschieden sind und Halogen, bevorzugt Cl oder F bedeuten oder

R⁸ NR¹⁰R¹¹, OH, OAlkali, OR⁷, O(i-C₃H₆), OCH₂CH₂OCH₃, SO₃H bedeutet und

R⁹ Halogen insbesondere Cl oder F oder Ammoniumsubstituent, insbesondere Trialkylammonium oder substituierte oder unsubstituierte Pyridinium- Substituenten, wie z.B.

bedeutet und

R¹⁰ Wasserstoff oder aliphatischer Rest, vorzugsweise C1-C4-Alkylrest, welcher durch OCH₃, OC₂H₅, COOH, OSO₃H, SO₃H, OCH₂CH₂SO₂CH₂CH₂OSO₃H, OCH₂CH₂SO₂CH=CH₂, OCH₂CH₂SO₂CH₂CH₂Cl, SO₂CH₂CH₂OSO₃H, SO₂CH=CH₂ substituiert sein kann, oder cycloaliphatischer Rest vorzugsweise 5- bis 6- gliedriger Cycloalkylrest oder araliphatischer Rest vorzugsweise Reste der Formel

bedeutet,

wobei p = 1-4 bedeutet und der Rest A beispielsweise durch Cl, NO₂, COOH, SO₃H, CH₃, OCH₃, SO₂CH₂CH₂OSO₃H,

SO₂CH=CH₂, CH₂SO₂CH₂CH₂OSO₃H, CH₂SO₂CH=CH₂ substituiert sein kann, und

R¹¹ die für R¹⁰ genannten Bedeutungen hat oder Phenylrest oder substituierter Phenylrest vorzugsweise durch Cl, NO₂, COOH, SO₃H, CH₃, OCH₃, SO₂CH₂CH₂OSO₃H, SO₂CH=CH₂, CH₂SO₂CH₂CH₂OSO₃H, CH₂SO₂CH=CH₂ substituierter Phenylrest bedeutet
oder R⁶

ist,
wobei

R¹², R¹³ und R¹⁴ gleich oder verschieden sind und Halogen vorzugsweise Cl oder F bedeuten,
bzw. R⁶ für den Fall, daß R⁵

bedeutet

oder

bedeutet und

o eine ganze Zahl von 0 bis 12 ist und

m 0 oder 1 ist, wobei

für o=0 auch m=0 gilt.

Preferably R ^{2 is the} same or different and means -R ³ _m - (CHR ⁴ ) _o -R ⁵ -R ⁶ , where

R ^{3 is the} same or different and O,

S, NH, or NR ⁷ means and

R ^{7 is the} same or different and is C ₁ -C ₆ alkyl and

R ^{4 is the} same or different and is H or OH and

R ⁵ NH, NR ⁷ , S, O, or

is particularly preferably O, and

R ⁶ in the event that R ⁵ denotes NH, NR ⁷ , S, or O either

is

wherein R ⁸ and R ^{9 are the} same or different and are halogen, preferably Cl or F or

R ⁸ denotes NR ¹⁰ R ¹¹ , OH, O alkali, OR ⁷ , O (iC ₃ H ₆ ), OCH ₂ CH ₂ OCH ₃ , SO ₃ H and

R ⁹ halogen in particular Cl or F or ammonium substituent, in particular trialkylammonium or substituted or unsubstituted pyridinium substituents, such as, for example

means and

R ^{10 is} hydrogen or an aliphatic radical, preferably C1-C4-alkyl radical, which is substituted by OCH ₃ , OC ₂ H ₅ , COOH, OSO ₃ H, SO ₃ H, OCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ OSO ₃ H, OCH ₂ CH ₂ SO ₂ CH = CH ₂ , OCH ₂ CH ₂ SO ₂ CH ₂ CH ₂ Cl, SO ₂ CH ₂ CH ₂ OSO ₃ H, SO ₂ CH = CH ₂ , or cycloaliphatic radical preferably 5- to 6- membered cycloalkyl radical or araliphatic radical, preferably radicals of the formula

means

where p = 1-4 and the radical A is, for example, Cl, NO ₂ , COOH, SO ₃ H, CH ₃ , OCH ₃ , SO ₂ CH ₂ CH ₂ OSO ₃ H,

SO ₂ CH = CH ₂ , CH ₂ SO ₂ CH ₂ CH ₂ OSO ₃ H, CH ₂ SO ₂ CH = CH ₂ may be substituted, and

R ^{11 has} the meanings given for R ¹⁰ or phenyl radical or substituted phenyl radical preferably by Cl, NO ₂ , COOH, SO ₃ H, CH ₃ , OCH ₃ , SO ₂ CH ₂ CH ₂ OSO ₃ H, SO ₂ CH = CH ₂ , CH ₂ SO ₂ CH ₂ CH ₂ OSO ₃ H, CH ₂ SO ₂ CH = CH ₂ substituted phenyl radical
or R ⁶

is
in which

R ¹² , R ¹³ and R ^{14 are the} same or different and are preferably halogen, Cl or F,
or R ⁶ in the event that R ⁵

means

or

means and

o is an integer from 0 to 12 and

m is 0 or 1, where

for o = 0 also m = 0 applies.

Particularly preferred cyclodextrin derivatives according to the invention are 2,4-dichloro-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-hydroxy-1,3,5-triazinyl-cyclodextrins (Sodium salts), 2-fluoro-4-hydroxy-1,3,5-triazinyl-cyclodextrins (Sodium salts), 2,4,5-trichloropyrimidyl cyclodextrins, 5-chloro-2,4-difluoropyrimidyl cyclodextrins, 6- (2,3-dichloro) quinoxalinoyl cyclodextrins, 5- (2,4-dichloro) pyrimidinoyl cyclodextrins, 2-amino-4-chloro-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-ethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-diethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-methoxy-1,3,5-triazinyl-cyclodextrins.

The invention further relates to methods for producing the Cyclodextrin derivatives according to the invention. The production takes place preferably by means of a method which thereby is characterized in that native α-, β- and / or γ-cyclodextrin and / or a suitable α-, β- and / or γ-cyclodextrin derivative in a suitable reaction medium in the presence an acid acceptor and optionally a surface active Medium in weakly acidic to strongly basic Environment at temperatures from -10 to + 70 ° C with suitable implemented nitrogen-containing heterocycles and, if necessary, subsequently in the neutral or weakly basic range if necessary with the help of a buffer in an otherwise known manner and way is worked up.

The cyclodextrin derivative obtained can then optionally by means of cleaning processes customary for cyclodextrin derivatives to be further cleaned up.

With the method according to the invention, cyclodextrin can be Get derivatives with stable C-O, C-S or C-N bonds, whereby no toxic compounds occur as in the known ones Process by reacting cyclodextrin with Epichlorohydrin. For example, in the implementation of cyclodextrin with cyanuric chloride only table salt and toxicologically much safer by-products.

Any cyclodextrins are suitable for the process according to the invention or cyclodextrin derivatives which have at least one free OH group / cyclodextrin molecule in at least one of the Have positions C2, C3, and / or C6 of anhydroglucose suitable. Cyclodextrin or cyclodextrin derivative do not have to meet special requirements in terms of purity. she are of commercial quality with a water content of 0 to 16% applicable.

Examples of cyclodextrin derivatives for the invention Production processes are suitable are cyclodextrin ethers or mixed ethers, cyclodextrin esters or mixed esters or mixed cyclodextrin ether / ester derivatives, in particular the derivatives of β-cyclodextrin mentioned.

Hydrophilic cyclodextrin derivatives with the following substituents are particularly suitable: (C ₁ -C ₄ ) -alkyl radical, preferably methyl or ethyl radical, particularly preferably methyl radical; (C ₂ -C ₆ ) hydroxyalkyl radical, preferably hydroxypropyl radical or hydroxybutyl radical, particularly preferably hydroxypropyl radical, (C ₃ -C ₆ ) oligohydroxyalkyl radical, preferably C ₃ -C ₄ , particularly preferably dihydroxypropyl radical, acetyl radical, propionyl radical, butyryl radical, preferably acetyl radical, propionyl radical , particularly preferably acetyl radical.

Derivatives with an average Degree of substitution per anhydroglucose (DS) of 0.3 - 2.0 particularly preferably from 0.6 to 1.8.

Ionic cyclodextrin derivatives with the following substituents are also particularly suitable: carboxyalkyl radical in the form of the free acid or as an alkali salt, sulfonic acid alkyl radical in the form of the free acid or as alkali salt, carboxyhydroxyalkyl radical in the form of the free acid or as alkali salt, sulfonic acid hydroxyalkyl radical in the form of the free acid or as Alkali salt, (C ₁ -C ₄ ) alkyl group, (C ₂ -C ₄ ) hydroxyalkyl group and sulfate group.

In these cyclodextrin derivatives, the is preferably average degree of substitution per anhydroglucose (DS) 0.3 - 2.0, particularly preferably 0.4 - 1.5, in particular 0.4-0.6.

Ionic cyclodextrin derivatives are also particularly suitable with oxalyl radical, malonyl radical, succinyl radical, glutaryl radical and / or adipinyl as substituents, preferably with an average degree of substitution per anhydroglucose (DS) from 0.3 to 2.0, particularly preferably 0.4-1.5, especially 0.4-0.8.

The preparation of the suitable cyclodextrin derivatives is known from the literature.

Nitrogen-containing ones are for use in the process according to the invention Heterocycles with at least two electrophiles Centers suitable.

wobei X und Y gleich oder verschieden sein können und Halogen, bevorzugt F oder Cl bedeuten und Z Halogen bevorzugt F oder Cl, OH, OLi, ONa, OK, OR⁷, SR⁷, oder NR¹⁰R¹¹ bedeutet, wobei die Reste R⁷ bis R¹¹ die bereits genannten Bedeutung haben.Examples of such heterocycles are 2,4,5,6-tetrachloropyrimidine, 2,4,6-trifluoro-5-chloropyrimidine (which can be prepared from 2,4,5,6-tetrachloropyrimidine by halogen exchange); 2,4-dichloropyrimidine-5-carboxylic acid chloride (can be prepared by methods known from the literature); 2,3-dichloroquinoxaline-6-carboxylic acid chloride (production according to KGKleb, E. Siegel, K. Sasse, Angew. Chem. 76, 423 (1964); Angew. Chem. Int. Ed. Engl. 3, 408 (1964) and the compounds of the formulas II shown below

where X and Y can be identical or different and are halogen, preferably F or Cl and Z is halogen preferably F or Cl, OH, OLi, ONa, OK, OR ⁷ , SR ⁷ , or NR ¹⁰ R ¹¹ , where the radicals R ⁷ to R ^{11 have} the meaning already mentioned.

Examples of compounds of formula II are 2,4,6-trichloro-1,3,5-triazine; 2,4,6-trifluoro-1,3,5-triazine; 2-amino-4,6-dichloro-1,3,5-triazine; 2,4-dichloro-6-methoxy-1,3,5-triazine; 2,4-dichloro-6-hydroxy-1,3,5-triazine, or that Sodium salt of this compound, 2,4-dichloro-6-ethylamino-1,3,5-triazine, 2,4-dichloro-6-diethylamino-1,3,5-triazine.

The compounds mentioned are commercially available or by known or analogous processes from 2,4,6-trichloro-1,3,5-triazine through implementation with the appropriate Nucleophiles available.

2,4,6-Trichlor-1,3,5-triazine: 2,4,6-trifluoro-1,3,5-triazine; 2-amino-4,6-dichloro-1,3,5-triazine; 2,4-dichloro-6-methoxy-1,3,5-triazine; 2,4-dichloro-6-hydroxy1,3,5-triazine, Sodium salt; 2,4,5,6-tetrachloropyrimidine; 2,4,6-trifluoro-5-chloropyrimidine; 2,4-dichloropyrimidine-5-carboxylic acid chloride or 2,3-dichloroquinoxaline-6-carboxylic acid chloride 2,4-dichloro-6-ethylamino-1,3,5-triazine, 2,4-dichloro-6-diethylamino-1,3,5-triazine used.

As a reaction medium for the process according to the invention preferably DMF (dimethylformamide), DMSO (dimethyl sulfoxide), Xylene, dioxane, acetone, methanol, ethanol, water, Toluene, methyl ethyl ketone or mixtures of these substances are suitable.

When reacting with 2,4,6-trihalo-1,3,5-triazines, preferably Cyanuric chloride, the heterocycle should be finely dispersed Form present, in the form of mixtures with organic Solvents or in water if necessary with the addition of a surface-active By means of a wetting agent.

Water or a water / acetone mixture is particularly preferred in a mixing ratio of 10: 1 to 2: 1.

Preferred acid acceptors in the process according to the invention one or more substances selected from the Group of alkali or alkaline earth hydroxides, alkali or Alkaline earth carbonates, alkali or alkaline earth hydrogen carbonates, Alkali hydrogen phosphates, amines, tert. Amines, pyridine suitable.

NaOH, KOH, sodium carbonate, potassium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, Disodium hydrogen phosphate, dipotassium hydrogen phosphate, pyridine, Triethylamine or collidine used.

The surface-active agent in the process according to the invention the agents customary for reactions with cyanuric chloride suitable. Examples of such agents are alkyl sulfates and ether sulfates as sodium, ammonium, lithium and triethanolammonium salts (available for example from Henkel, Düsseldorf under the name Texapon), or Nonylphenol polyglycol ether or mixtures of anionic and nonionic surfactants (available for example from from Atlas Chemie, Essen under the name Renex and Atlox) or alkyl sulfonates.

Texapon K12, Renex 697 and Atlox are particularly suitable 4853B, sodium dodecyl sulfate, sodium octyl sulfate, 1-dodecane sulfonic acid sodium salt, 1-octanesulfonic acid sodium salt (The latter is available, for example, from Fluka Feinchemischen GmbH, Neu-Ulm).

Common buffers are used as buffers in the process according to the invention for the pH range from 6 to 10, preferably 7 to 9. Such buffers are, for example, phosphate buffers (e.g. Na ₂ HPO ₄ / KH ₂ PO ₄ ), carbonate buffers (e.g. Na carbonate / Na bicarbonate), acetate buffers (e.g. acetic acid / Na acetate), citrate buffers (e.g. citric acid / Na citrate) or Tris buffer (e.g. trishydroxymethylaminomethane / HCl).

Cyclodextrin is preferred per mole of anhydroglucose 0.1-4 mol, preferably 0.2-2 mol, particularly preferably 0.3-1.2 mol, nitrogen-containing heterocycle used. The used Molar ratios are depending on the desired Degree of substitution and water content of the cyclodextrin used chosen.

Preferably, per mole of nitrogen-containing heterocycle 0.5-3 mol, acid acceptor used.

For the preparation of monohalotriazinyl-cyclodextrin derivatives 2,4,6-trihalo-1,3,5-triazines become 1.5-4 mol, preferably 1.75-3.5 mol, particularly preferably 1.8-3.2 mol, Acid acceptor used per mole of nitrogen-containing heterocycle.

For the preparation of monohalotriazinyl-cyclodextrin derivatives dihalo-1,3,5-triazines are preferably 0.5-2 mol 0.75-1.5 mol, particularly preferably 0.8-1.3 mol, acid acceptor used per mole of nitrogen-containing heterocycle.

For the preparation of trihalopyrimidyl cyclodextrin derivatives be 0.5-1.5 mol, preferably 0.75-1.25 mol, particularly preferably 0.8-1.2 mol, acid acceptor per mol nitrogenous Heterocycle used.

For the preparation of dichloro-quinoxalinoyl or dichloropyrimidinoyl cyclodextrin derivatives be 0.5-2 mol, preferably 0.75-1.5 mol, particularly preferably 0.8-1.3 mol, Acid acceptor used per mole of nitrogen-containing heterocycle.

Cyclodextrin or cyclodextrin derivative are preferred and reaction medium in a cyclodextrin / reaction medium ratio from 1:30 to 1: 1.5, preferably about 1:14 to 1: 2, particularly preferably 1:12 to 1: 3, used.

For the preparation of the cyclodextrin derivatives according to the invention become cyclodextrin or cyclodextrin derivative, nitrogenous Heterocycle, acid acceptor, reaction medium and if necessary, surface-active agent in the specified proportions combined either simultaneously or in succession and stirred well.

In the process according to the invention it is important that the reaction medium doesn't get too sour.

The method according to the invention should be used in the implementation of Cyclodextrin or cyclodextrin derivative with trihalotriazine for Preparation of monohalotriazinyl cyclodextrins at -10 ° C to 35 ° C, preferably -5 ° C to 25 ° C, particularly preferably -5 ° C up to 15 ° C.

The implementation of cyclodextrin or cyclodextrin derivative with Trihalotriazine for the preparation of dihalotriazinyl-cyclodextrins, should be at -10 ° C to 25 ° C, preferably -5 ° C to 10 ° C, particularly preferably -5 ° C to 5 ° C, take place.

The implementation of cyclodextrin or cyclodextrin derivative with Tetrahalopyrimidine, at 10 ° C to 45 ° C, should be preferred 15 ° C to 35 ° C, particularly preferably 20 ° C to 35 ° C, take place.

The implementation of cyclodextrin or cyclodextrin derivative with heterocyclic acid chlorides takes place at temperatures of 20 to 90 ° C, especially at 30 to 80 ° C, especially at 40 up to 70 ° C.

The method according to the invention is advantageously used in Normal pressure carried out.

The response times are usually between 0.5 and 6 h, often between 2-4 h.

The process according to the invention preferably gives mixtures of cyclodextrin derivatives having an average degree of substitution (DS) for R ¹ of 0 to 2.0, depending on the cyclodextrin / cyclodextrin derivative used as starting product and a (DS) for R ² of 0.1 to 3, 0.

The determination of the average degree of substitution per anhydroglucose (DS value) for nitrogen-containing substituents can be carried out using elementary analysis using methods known from the literature, such as in US 5,134,127 and US 3,453,257 for sulfur- or nitrogen-containing substituents described.

The reactive centers per anhydroglucose can be determined by reacting the derivatives according to the invention with nucleophiles, as described in the examples with chlorine as a leaving group as DS _Cl .

A further workup of the derivatives according to the invention can, if desired, be used for cyclodextrin cleaning generally known methods. Such methods are for example: precipitation using alcohol / water mixtures, direct crystallization, adsorption chromatography or Gel permeation chromatography and dialysis.

The monochlorotriazinyl-cyclodextrin derivatives according to the invention dissolved in water, you observed one slow hydrolysis with elimination of HCl. The emerging Acid was autocatalytic. In buffer solutions with a pH from 7 to 9, preferably about 8, the hydrolysis of the Triazinyl-cyclodextrin derivatives according to the invention prevented become. In such aqueous solutions are those according to the invention Cyclodextrin derivatives have a shelf life of at least 6 weeks.

The invention therefore also relates to solutions with a pH from 7 to 9 containing cyclodextrin derivatives according to the invention.

The cyclodextrin derivatives according to the invention are in able with any connections that have one or more nucleophilic groups such as OH, NH or SH groups contribute to react with formation of covalent bonds. The invention therefore also relates to compositions which the cyclodextrin derivatives according to the invention in bound Form included. Depending on the type of connection or according to the number of nucleophilic groups in the compound with the cyclodextrin derivatives according to the invention the preparation of new cyclodextrin derivatives, cyclodextrin oligomers, or cyclodextrin polymers are also possible such as the binding of cyclodextrins or cyclodextrin derivatives of polymers or a surface modification.

The production of new cyclodextrin derivatives containing ether can be carried out, for example, by reacting the cyclodextrin derivatives according to the invention with C ₁ to C ₆ alcohols, for example methanol, ethanol, 2-methoxyethanol or isopropanol, under slightly alkaline conditions at 40 to 100 ° C.

By implementing the cyclodextrin derivatives according to the invention with thiols such as Ethanethiol or propanethiol can be Prepare thioether-containing cyclodextrin derivatives.

By implementing the cyclodextrin derivatives according to the invention with primary or secondary amines, for example alkyl amines such as methyl or dimethylamine, ethyl or diethylamine, Aniline or aniline derivatives, or hydroxyalkylamines such as morpholine or morpholine derivatives can be basic Represent cyclodextrin derivatives.

By reaction with tertiary amines such as trimethylamine, Triethylamine, pyridine or pyridine derivatives such as for example nicotinic acid or nicotinic acid derivatives, or Diazabicyclooctane can be positively charged cyclodextrin derivatives, which are themselves reactive cyclodextrin derivatives are represent.

Cyclodextrin oligomers or cyclodextrin polymers can be using the cyclodextrin derivatives according to the invention for example, as follows:

By implementing the invention Cyclodextrin derivatives with compounds that have two or more wear nucleophilic groups, the Cyclodextrin derivatives or for the formation of nucleophiles, the wear the nucleophilic group on a spacer. As examples for compounds that have two or more nucleophilic groups wear di- or oligo alcohols such as 1,3-diaminopropane, 1,4-diaminobutane, 1,3-propanediol, 1,4-butanediol, Aminobutanol, di- or oligoamines, di- or Oligothiols or mixed nucleophiles such as amino alcohols, etc. or also cyclodextrins / derivatives or those according to the invention Cyclodextrin derivatives themselves.

If the reactions are carried out in high dilution, so non-crosslinked cyclodextrin derivatives are also obtained, which is a nucleophilic group e.g. OH, NH or SH on one Contain spacers, so they are nucleophiles themselves.

By implementing the cyclodextrin derivatives according to the invention with soluble polymers or biopolymers like for example α, β, γ-cyclodextrin, α, β, γ-cyclodextrin derivatives, Starch or starch derivatives, polyvinyl alcohol (PVA) or PVA derivatives, polyallylamines, oligomeric sugars or Sugar derivatives can be modified polymers, which in are able to solubilize substances that are sparingly soluble in water, produce.

The substances thus obtained can be, for example, as Use selective separating agents in chromatography.

By implementing the cyclodextrin derivatives according to the invention with insoluble polymers or biopolymers, which carry nucleophilic groups such as cellulose or cellulose derivatives, polymeric sugar or sugar derivatives, Chitin, gelatin, polyvinyl alcohols or their derivatives, or polyallylamines, modified polymers, which are capable of sparingly water-soluble substances solubilize, represent.

The substances thus obtained can be, for example, as Use selective separating agents in chromatography.

The present invention further relates to polymers to which covalently 0.1 to 100% by weight of at least one according to the invention Cyclodextrin derivative with at least one nitrogenous Heterocycle is bound.

0.3 to 25% by weight of said cyclodextrin derivative is preferred bound to the polymer.

The connection is preferably made in the outside areas of the polymer.

The polymers covalently equipped with CD have a wide variety beneficial properties.

• die Verbesserung der Haftung auf Oberflächen
• die Solubilisierung des Polymeren/Oligomeren in der entsprechenden Matrix
• die Hydrophilisierung bzw. Hydrophobisierung des Polymeren
• die Verbesserung der Benetzbarkeit, Erhöhung der Verträglichkeit mit dem umgebenden Medium
• Erhöhung der Stabilität gegen Koagulation, mit CD ausgerüstete Polymere bilden stabilere Emulsionen
• Rheologieänderung
• die Verbesserung der Filmbildung
• bei Copolymerisation von Styrol/Butylacrylat mit wasserlöslichen Hilfsmonomeren werden häufig wasserlösliche Oligomere gebildet. Durch das mit CD ausgerüstete Polymer werden diese Oligomere gebunden. Aufgrund der nun niedrigeren Viskosität kann der Feststoffgehalt der Dispersion angehoben werden. Durch das Binden dieser Oligomere wird ferner deren weichmachende Wirkung beseitigt, die Mindestfilmbildungstemperatur wird dadurch angehoben
• die mit CD ausgerüsteten Polymere sind deutlich weniger wasseranfällig

The CD's can themselves have effects on the properties of the polymer, for example the CD's cause:

• improving adhesion to surfaces
• the solubilization of the polymer / oligomer in the corresponding matrix
• the hydrophilization or hydrophobization of the polymer
• improving wettability, increasing compatibility with the surrounding medium
• Increased stability against coagulation, CD-treated polymers form more stable emulsions
• Rheology change
• the improvement of film formation
• When styrene / butyl acrylate is copolymerized with water-soluble auxiliary monomers, water-soluble oligomers are often formed. These oligomers are bound by the polymer equipped with CD. Due to the now lower viscosity, the solids content of the dispersion can be increased. By binding these oligomers, their softening effect is also eliminated, and the minimum film formation temperature is increased
• the polymers equipped with CD are significantly less susceptible to water

• es können Wirkstoffe in das CD eingeschlossen und kontrolliert freigesetzt werden. Das CD wirkt dann wie ein Haftvermittler. Beispiele für Wirkstoffe sind: Biozide, Insektizide, Fungizide, Herbizide, Pheromone, Duftstoffe, Geschmacksstoffe, pharmazeutische Wirkstoffe, Wirkstoffe zur Antistatikausrüstung oder Flammschutzausrüstung, Stabilisatoren (UV), Farbstoffe.
• Wirkstoffe können durch den Einschluß stabilisiert (gegen Licht, Temperatur, Oxidation, Hydrolyse, Verdampfung), solubilisiert und damit (bio-)verfügbar gemacht oder kontrolliert freigesetzt werden. Der Vorteil dabei ist, daß die Wirkstoffe unmittelbar am Polymer gebunden und kompatibilisiert sind. Es muß keine Fremdsubstanz zugemischt werden, die später ausbluten kann.
• ungewünschte Substanzen können absorbiert werden
• Substanzen können selektiv absorbiert werden. Die CD-ausgerüsteten Polymere sind somit auch als Trennmaterialien geeignet.
• bei mit CD ausgerüsteten Polymeren wird ein Ausblühen von nicht kovalent gebundenen Hilfsstoffen verhindert. Die Hilfsstoffe werden homogener eingearbeitet. Beispielsweise werden Vernetzer (z.B. AlCl₃, Al(OH)₃, B(OH)₃) homogener eingearbeitet. Die Einarbeitungszeiten können verkürzt werden.
• die so formulierten Wirkstoffe sind deutlich weniger toxisch als die freien Verbindungen. Beispielsweise sind Isothiazolone/Chloracetamid in Form der CD-Komplexe weniger hautreizend.
• die im Polymer enthaltenen Restmonomeren (Vinylacetat, insbesondere wasserunlösliche Monomere, welche schlecht einpolymerisieren, wie beispielsweise Vinyllaurat, Versaticsäurevinylester, Butylacrylat) werden komplexiert. Durch die Komplexierung wird deren Freisetzung verzögert, so daß beispielsweise eine Dispersion gefahrlos verarbeitet werden kann. Beispielsweise werden die MAK-Werte unterschritten.
• geruchsbelästigende Substanzen, wie z.B. Abbauprodukte, Nebenprodukte von Polymeren, wie z.B. Amine, Essigsäure, etc. werden komplexiert.

The CD cavity can be used in a variety of ways, and various new effects have been observed:

• Active ingredients can be included in the CD and released in a controlled manner. The CD then acts as an adhesion promoter. Examples of active ingredients are: biocides, insecticides, fungicides, herbicides, pheromones, fragrances, flavorings, pharmaceutical active ingredients, active ingredients for antistatic or flame retardant equipment, stabilizers (UV), dyes.
• Active ingredients can be stabilized by inclusion (against light, temperature, oxidation, hydrolysis, evaporation), solubilized and thus made (bio) available or released in a controlled manner. The advantage here is that the active ingredients are bound directly to the polymer and are compatibilized. No foreign substance has to be added that can bleed out later.
• unwanted substances can be absorbed
• Substances can be absorbed selectively. The CD-equipped polymers are therefore also suitable as release materials.
• in the case of polymers equipped with CD, blooming of non-covalently bound auxiliaries is prevented. The auxiliaries are incorporated more homogeneously. For example, crosslinkers (eg AlCl ₃ , Al (OH) ₃ , B (OH) ₃ ) are incorporated more homogeneously. The training periods can be shortened.
• the active ingredients formulated in this way are significantly less toxic than the free compounds. For example, isothiazolones / chloroacetamide in the form of the CD complexes are less irritating to the skin.
• The residual monomers contained in the polymer (vinyl acetate, especially water-insoluble monomers which do not polymerize well, such as vinyl laurate, vinyl versatic acid, butyl acrylate) are complexed. The complexation delays their release, so that, for example, a dispersion can be processed safely. For example, the MAK values are undercut.
• odor-causing substances, such as degradation products, by-products of polymers, such as amines, acetic acid, etc. are complexed.

Examples of polymers suitable according to the invention are polymers with at least one nucleophilic group.

Examples of synthetic polymers are polyesters, polyamides, Polyamines, phenoplasts, aminoplasts, polyurethanes, polyacrylic acids, Polyacrylamides, polyallyl alcohols, polyallylamines, Polyvinyl acetate polymers, polyvinyl alcohols, polyepoxides, Silicones, polypropylene, polyethylene.

These must carry at least one nucleophilic group. Examples for nucleophilic groups are: -OH, -NH or SH groups.

The polymers can be produced by polycondensation, Polyaddition, radical polymerization with the help different polymerization techniques:

Examples of the reaction in a homogeneous phase are solvent polymerization or bulk polymerization.

Examples of the reaction in the heterogeneous phase are Precipitation polymerization, suspension polymerization, the Emulsion polymerization and interfacial polycondensation.

Natural polymers with are also suitable according to the invention at least one nucleophilic group, such as: Polysaccharides, e.g. Starch, glycogens, mannans, pectins, Chitins and derivatives or proteins, e.g. Proteins, collagen, Elastin, globulins, fibrinogens, wool, silk, polyglutamate, Gelatin or polyisoprene or polynucleotide or lignin or lignin-containing substances.

The invention further relates to methods for producing the polymers according to the invention.

A) Die Ausrüstung eines fertigen Polymeren. Das Polymere sollte im Reaktionsmedium nach Möglichkeit löslich, gut gequollen oder gut benetzt vorliegen. Bei der Ausrüstung von fertigen Polymeren können vorzugsweise folgende Verfahren unterschieden werden

A1) Flotte-Verfahren. Die Ausrüstung des Polymeren erfolgt in der Flotte:
Das Polymer wird im Lösungsmittel suspendiert gequollen oder gelöst und mit dem reaktionsfähigen (elektrophilen) CD in Gegenwart eines Säureakzeptors umgesetzt.

A2) Tauchverfahren: Das Imprägnieren des Polymeren erolgt in der Flotte, die Fixierung außerhalb der Flotte. Dies Verfahren geht nur bei im Reaktionsmedium unlöslichen Polymeren:
Das Polymer wird in die Flotte (bestehend aus Lösungsmittel, reaktionsfähigem CD und Säureakzeptor) bei RT oder bei erhöhter Temperatur eingetaucht, gut imprägniert anschließend aus der Flotte entfernt und bei erhöhter Temperatur fixiert und getrocknet.

B) die Ausrüstung von Polymeren erfolgt während der Polymerisation. Die Polymerisation kann durchgeführt werden:

in homogener Phase
(Lösungspolymerisation oder Polymerisation in Substanz)

in heterogener Phase
(Fällungspolymerisation, Suspensionspolymerisation, Emulsionspolymerisation oder Grenzflächenpolykondensation)

The following processes for producing polymers according to the invention with CD can be distinguished:

A) The finishing of a finished polymer. If possible, the polymer should be soluble, well swelled or well wetted in the reaction medium. When finishing finished polymers, the following processes can preferably be distinguished

A1) Fleet process. The polymer is finished in the fleet:
The polymer is suspended, swollen or dissolved in the solvent and reacted with the reactive (electrophilic) CD in the presence of an acid acceptor.

A2) Immersion process: The impregnation of the polymer takes place in the liquor, the fixation outside the liquor. This process only works with polymers that are insoluble in the reaction medium:
The polymer is immersed in the liquor (consisting of solvent, reactive CD and acid acceptor) at RT or at elevated temperature, then well impregnated, removed from the liquor and fixed and dried at elevated temperature.

B) The finishing of polymers takes place during the polymerization. The polymerization can be carried out:

in a homogeneous phase
(Solution polymerization or bulk polymerization)

in a heterogeneous phase
(Precipitation polymerization, suspension polymerization, emulsion polymerization or interfacial polycondensation)

In this case, the polymerization is in equilibrium reactive CD's and an acid acceptor performed.

As cyclodextrin derivatives with a nitrogen-containing heterocycle to finish the polymer, the invention Cyclodextrin derivatives used.

The following cyclodextrin derivatives are particularly preferred Equipment of textile materials or leather used: 2,4-dichloro-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-hydroxy-1,3,5-triazinyl-cyclodextrins (Sodium salts), 2-fluoro-4-hydroxy-1,3,5-triazinyl-cyclodextrins (Sodium salts), 2,4,5-trichloropyrimidyl cyclodextrins, 5-chloro-2,4-difluoropyrimidyl cyclodextrins, 6- (2,3-dichloro) quinoxalinoyl cyclodextrins, 5- (2,4-dichloro) pyrimidinoyl cyclodextrins, 2-amino-4-chloro-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-ethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-diethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-methoxy-1,3,5-triazinyl-cyclodextrins.

2-Chloro-4-hydroxy-1,3,5-triazinyl-β-cyclodextrin is particularly preferred (MCT-β-CD) used.

Cyclodextrin derivatives with a DS are preferred (average degree of substitution per anhydroglucose) to DS 3.0, particularly preferably DS 0.1 to 2.0, in particular preferably DS 0.3 to 1.0 for reaction with the polymers used.

In addition to the cyclodextrin derivatives according to the invention and those already The polymers mentioned are the following starting materials in the invention Process used.

Acid acceptors:

one or more substances selected from the group of Alkali or alkaline earth hydroxides, alkali or alkaline earth hydrogen carbonates, Alkali hydrogen phosphates, amines, tert. Amines, Pyridine or mixtures of these substances.

The following are particularly suitable: NaOH, KOH, sodium carbonate, potassium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, Disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium acetate, Potassium acetate, pyridine, triethylamine or collidine, NaOH and sodium carbonate are particularly preferred.

Solvent:

Toluene, xylene, acetonitrile, acetone, THF, methanol, ethanol, Propanol, butanol, dioxane, formamide, methylformamide, dimethylformamide, N-methylpyrrolidone, DMPU (1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) pyrimidone), Acetamide, methylacetamide, Dimethylacetamide, DMSO or mixtures of these substances.

Water and alcohols or mixtures are particularly preferred suitable. Water is particularly preferred. It is but also possible to work in substance.

Additions:

Urea, alginate

Salts

Alkali chlorides, alkali sulfates, ammonium sulfate, preferably Sodium chloride, sodium sulfate, ammonium sulfate.

The components mentioned are preferably in the following Quantity ratios used:

CD concentration in the liquor (weight percent) 0.5-70%, preferably 3-50%, particularly preferably 5-30%.

Salt concentration in the liquor (percent by weight) 0-30%, preferred 0 to 20%, particularly preferably about 10%.

Additional concentration 0-30%, particularly preferably 0-20%.

Base concentration in the liquor (weight percent) 0.2-30%, particularly preferably 0.5-10%.

Alkaline reinforcement in the fleet when using carbonates as base (NaOH%) 0.1 to 3%, preferably 0.3 to 1%.

Molar ratios:

"active chlorine" / acid acceptor = 2: 1 to 1:10, preferably 1: 1 to 1: 3 active (electrophilic reacting) Chlorine is determined by reaction with diethylamine as described in Example 10.

The reaction takes place at a temperature of 0 ° C to 170 ° C, preferably between 20 ° C and 100 ° C, particularly preferably between 40 and 98 ° C. The temperature is in Dependence on the reactivity of the reactants to choose.

The reaction is preferably carried out at normal pressure to slight overpressure (e.g. own pressure when using closed Apparatus).

The reaction times are usually between 5 min and 6 h, often between 0.5 - 4 h.

a) in homogener Form z.B. als polymerer Werkstoff oder Harz

b) in heterogener Form z.B. als Suspension oder Emulsion anfallen.

The polymers according to the invention can

a) in homogeneous form, for example as a polymeric material or resin

b) are obtained in heterogeneous form, for example as a suspension or emulsion.

Aqueous polymer dispersions according to the invention can by Spray drying can be atomized and used in powder form become.

The polymers according to the invention are suitable for all applications which are known for polymers. They are suitable, for example as a polymeric material. The invention Polymers are also suitable for all applications for Cyclodextrins are known.

Aqueous polymer dispersions according to the invention are suitable especially as coating agents and adhesives, for example for paper, textiles, glass fibers, wood and cardboard.

Aqueous polymer dispersions with are particularly suitable a solids content of 30 to 75%, which with cyclodextrin derivatives of the general formula (I) are modified, containing Homo- or copolymers of ethylenically unsaturated monomers.

Such aqueous polymer dispersions are obtainable from Emulsion polymerization of one or more ethylenically unsaturated Monomers containing reactive groups and possibly an emulsifier using free radical initiators in an aqueous medium, in the presence of cyclodextrin derivatives of the general Formula I.

• als Bindemittel in der Papierherstellung,
• als Bindemittel zur Herstellung von Wirkstoffe enthaltenden, bevorzugt durch Direktverpressung hergestellten Preßkörpern
• als Klebstoffe für Holz, Papier, Textilien,
• als Bindemittel für Beschichtungen, Putze und Anstriche, insbesondere Anstrichfarben,
• in der Bauindustrie, insbesondere als Zusätze zu hydraulischen Bindemitteln wie Zement und Gips,
• insbesondere in Beton, Bauklebern, Mörteln, Spachtelmassen und Verlaufmassen.

Typical applications of the aqueous polymer dispersions or dispersion powders in these areas are the use

• as a binder in papermaking,
• as binders for the production of active substances containing, preferably produced by direct pressing
• as adhesives for wood, paper, textiles,
• as binders for coatings, plasters and paints, especially paints,
• in the construction industry, especially as additives to hydraulic binders such as cement and gypsum,
• especially in concrete, building adhesives, mortars, leveling compounds and leveling compounds.

The polymers of the invention, or one with the inventive Polymer dispersions coated paper, textile, Glass fiber, wood and cardboard show increased hydrophobicity on. With strong equipment, the materials have a higher Stiffness.

Paper, textiles, fiberglass, wood and cardboard can be used Active ingredients, e.g. with fragrances, UV stabilizers, Biocides, bactericides, insecticides, fungicides, Pheromones. With objects equipped in this way can cause unpleasant smells (e.g. sweat, acetic acid, butyric acid, Amines, sulfur compounds or residual monomers more toxic Substances) are retained. This can advantageous for example during the Processing / application of these materials.

The CD-modified polymers according to the invention can be for all applications known for cyclodextrins. are use.

• die Solubilisierung von in Wasser nicht- oder schwerlöslichen Substanzen, z.B. von Wirkstoffen, wie Bioziden, Pharmakas, Stabilisatoren
• die Erhöhung der Bioverfügbarkeit von Wirkstoffen
• die Stabilisierung von Substanzen gegen Licht, Temperatur, Oxidation, Hydrolyse oder von flüchtigen Substanzen
• die Maskierung von schlechtem Geschmack oder unangehnemem Geruch
• die kontrollierte Abgabe von Wirkstoffen wie Bioziden, Pharmaka
• die selektive Extraktion oder Komplexierung von Verbindungen (Trennungen)
• die Formulierung von Wirkstoffen, z.B. als pulverförmige Formulierung.

Examples include:

• the solubilization of water-insoluble or sparingly soluble substances, for example active substances such as biocides, pharmaceuticals, stabilizers
• increasing the bioavailability of active ingredients
• the stabilization of substances against light, temperature, oxidation, hydrolysis or of volatile substances
• masking bad taste or unpleasant smell
• the controlled release of active ingredients such as biocides, pharmaceuticals
• the selective extraction or complexation of compounds (separations)
• the formulation of active ingredients, for example as a powder formulation.

By linking the cyclodextrin derivatives according to the invention surfaces bearing on nucleophilic groups these surfaces can be modified. For example the cyclodextrin derivatives according to the invention react with paper, pigments, gelatin or leather. The products thus obtained can be e.g. as an adhesion promoter, to increase hydrophilicity or to complex Use substances that are sparingly soluble in water.

After implementation with textiles such as cotton, wool, natural or synthetic fibers etc. can be on the Surface of the textiles thus treated in each case desired Complex connections. For example, the complexation of Biocides, UV stabilizers or fragrances on the textiles possible.

The present invention further relates to textile material, in particular a fiber, a filament, a yarn, a pile or a fabric, or leather, which with 0.1 up to 25% by weight, based on the weight of the untreated Material, at least one cyclodextrin derivative according to the invention is equipped.

The textile material or leather is preferably 0.3 to 10% by weight of the cyclodextrin derivative mentioned.

The equipment is preferably in the outdoor areas of the Fibers or the material.

The equipment is made via covalent bonding of the invention Cyclodextrin derivatives. This causes a big one Wet fastness and wash resistance.

The finishing of textile materials or leather with Cyclodextrin derivatives according to the invention with at least one The nitrogen-containing heterocycle is analogous to that in the textile / leather industry usual methods for reactive dyes with the corresponding reactive groups.

Examples of suitable textile materials for finishing are:

Cellulose fibers, especially cotton, regenerated cellulose (e.g. viscose or copper artificial silk), fiber blends with Cellulose or wool, especially sheep's wool, as well as polymer fibers such as polyester, polyamide or polyacrylonitrile with at least a nucleophilic group such as OH, SH or NH or Fiber blends with these polymer fibers.

The invention further relates to methods for producing the materials according to the invention. The production is preferably carried out by means of a method which is characterized in that is that cyclodextrin derivatives according to the invention, which follow are described in more detail in a suitable reaction medium (Liquor) with the addition of bases and possibly of Salts and additives to the reaction medium dissolved, in neutral to basic milieu applied to the materials or leather, the materials or the leather may have dried and then be fixed at temperatures of 20-220 ° C.

Applying the fleet to the materials or leather can be done in a batch process (pull-out process) the fixation is done by heating the liquor or in semi-continuous dwell process or in continuous Procedures in which the fixation outside the fleet on the (impregnated), possibly dried, soaked in the liquor Material is made in the same way as for dyeing textiles Materials or leather developed dyeing techniques. Especially Fixation becomes efficient with the last two Procedure if the textile material before fixing through Squeezing largely freed from the liquor or even dried has been. Then there is a thorough rinsing the materials with cold and / or hot water and possibly washing the materials with an effective detergent at the appropriate temperature in an otherwise known manner and Wise.

As cyclodextrin derivatives with nitrogenous Heterocycle to equip the textile material or The cyclodextrin derivatives according to the invention become leather used.

The following cyclodextrin derivatives are particularly preferred Equipment of textile materials or leather used: 2,4-dichloro-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-hydroxy-1,3,5-triazinyl-cyclodextrins (Sodium salts), 2-fluoro-4-hydroxy-1,3,5-triazinyl-cyclodextrins (Sodium salts), 2,4,5-trichloropyrimidyl cyclodextrins, 5-chloro-2,4-difluoropyrimidyl cyclodextrins, 6- (2,3-dichloro) quinoxalinoyl cyclodextrins, 5- (2,4-dichloro) pyrimidinoyl cyclodextrins, 2-amino-4-chloro-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-ethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-diethylamino-1,3,5-triazinyl-cyclodextrins, 2-chloro-4-methoxy-1,3,5-triazinyl-cyclodextrins.

2-Chloro-4-hydroxy-1,3,5-triazinyl-β-cyclodextrin is particularly preferred (HCT-β-CD) used.

Cyclodextrin derivatives with a DS are preferred (average degree of substitution per anhydroglucose) to DS 3.0, particularly preferably DS 0.2 to 2.0, in particular preferably DS 0.3 to 1.0 for reaction with the textile Material or leather used.

The cyclodextrin derivatives according to the invention are analogous to the reactive ones Dyes applied to the fiber or leather. Man preferably uses those in the dyeing with reactive dyes usual dyeing machines. One differentiates each for reactivity between cold fixers and hot fixers. These differ in the reactivity of the reactive Group.

Cold fixers include cyclodextrin derivatives with dichlorotriazine, Monofluorotriazine, dichloroquinoxaline, difluorochloropyrimidine and vinyl sulfone groups, to the heat fixers the monochlorotriazines and the trichloropyrimidines.

The cyclodextrin derivative which is particularly preferred according to the invention 2-chloro-4-hydroxy-1,3,5, -triazinyl-ß-cyclodextrin, Sodium salt (MCT-β-CD) therefore belongs to the group of heat fixers and is therefore somewhat reactive.

For the finishing of leather are especially the di and Monochlorotriazine, pyrimidine cyclodextrin derivatives or Cyclodextrin derivatives with vinyl sulfonic acid groups are suitable.

A suitable dyeing technique is, for example, in Ullman's Encyclopedia of Industrial Chemistry 5th edition, Vol. A 22, page 662.

For finishing textile materials or leather with A distinction is made between the cyclodextrin derivatives according to the invention 3 Fixing procedure:

1. Extraction process or batch process

With this process, loose materials such as yarn or Piece goods treated (e.g. textile fabrics: yarn, knitted and Knitwear, pile fabrics, terry goods, fiber blends). The cyclodextrin derivatives are applied in the Brine by heating. Bases and possibly salts and additives are either completed at the start of the fleet process added or during the process in portions according to certain Time and at a certain temperature added.

20-60°C, vorzugsweise 30-50°C

pH = 9-12, vorzugsweise pH = 10-11

Gesamtreaktionszeit 0,1-4 h, vorzugsweise 0,2 - 2 h.

Reaction parameters for the cold fixers

20-60 ° C, preferably 30-50 ° C

pH = 9-12, preferably pH = 10-11

Total reaction time 0.1-4 hours, preferably 0.2-2 hours.

pH = 10-13, vorzugsweise pH = 11-12

Gesamtreaktionszeit bei einer Fixiertemperatur von 90-98°C, 0,1-4 h, vorzugsweise 0,2-1,5 h

Gesamtreaktionszeit bei einer Fixiertemperatur um 25°C, 5-40 h, vorzugsweise 7-25 h.

Reaction parameters for the heat fixers such as MCT-β-CD 20-100 ° C, preferably 50-98 ° C

pH = 10-13, preferably pH = 11-12

Total reaction time at a fixing temperature of 90-98 ° C, 0.1-4 h, preferably 0.2-1.5 h

Total reaction time at a fixing temperature around 25 ° C, 5-40 h, preferably 7-25 h.

2. Semi-continuous dwell process

This process is used to treat piece goods (e.g. cellulose piece goods). The material is impregnated with the fleet, fixation takes place outside the liquor at room temperature or by heating after the textile material has passed through Squeeze dried to a certain liquor content has been.

pH = 9-12, vorzugsweise pH = 10-11

Verweildauer bei 18-60°C, vorzugsweise 20-40°C außerhalb der Flotte 1-10 h, vorzugsweise 2-8 h.

Reaction parameters for the cold fixers

pH = 9-12, preferably pH = 10-11

Residence time at 18-60 ° C, preferably 20-40 ° C outside the liquor 1-10 h, preferably 2-8 h.

pH=10-13, vorzugsweise pH = 11-12

Gesamtreaktionszeit bei einer Fixiertemperatur von 90-98°C, 0,1- 4 h, vorzugsweise 0,2 - 1,5 h

Gesamtreaktionszeit bei einer Fixiertemperatur um 25°C, 5-40 h, vorzugsweise 7-25 h.

Reaction parameters for the heat fixers such as MCT-β-CD 20-100 ° C, preferably 50-98 ° C

pH = 10-13, preferably pH = 11-12

Total reaction time at a fixing temperature of 90-98 ° C, 0.1-4 h, preferably 0.2-1.5 h

Total reaction time at a fixing temperature around 25 ° C, 5-40 h, preferably 7-25 h.

3. Continuous process

In this process, piece goods (e.g. cellulose piece goods) Equipped and washed in one operation. The Material comes with the liquor (cyclodextrin derivative, base if necessary salt and additives) impregnated and then dried. Subsequent treatment at a higher temperature by treatment with hot air or saturated steam or by contact heat is fixed. Rinse and wash the material ends the finishing process. Heat fixers are preferred like MCT-β-CD.

pH = 9-12, vorzugsweise pH = 10-11

Verweildauer bei 18-60°C, vorzugsweise 20-40°C, 1-10 h, vorzugsweise 2-8 h.

Fixierung bei 90-160°C, vorzugsweise 100-140°C

Fixierdauer 5-180 s, vorzugsweise 10-100 s

Reaction parameters for the cold fixers

pH = 9-12, preferably pH = 10-11

Residence time at 18-60 ° C, preferably 20-40 ° C, 1-10 h, preferably 2-8 h.

Fixation at 90-160 ° C, preferably 100-140 ° C

Fixing time 5-180 s, preferably 10-100 s

Fixierung bei 20-100°C, vorzugsweise 50-98°C, für 0,1-4 h, vorzugsweise 0,2-1,5 h. Die Fixierdauer bei einer Temperatur um 25°C beträgt 5-40 h, vorzugsweise 7-25 h.

Fixierung bei 100 - 230°C, vorzugsweise 140-220°C Fixierdauer 10-900 s, vorzugsweise 16-600 s

Reaction parameters for the heat fixers such as MCT-β-CD pH = 10-13, preferably pH = 11-12

Fixation at 20-100 ° C, preferably 50-98 ° C, for 0.1-4 h, preferably 0.2-1.5 h. The fixing time at a temperature around 25 ° C is 5-40 h, preferably 7-25 h.

Fixation at 100 - 230 ° C, preferably 140-220 ° C fixation time 10-900 s, preferably 16-600 s

Preferred solvents in the process according to the invention Water or softened water is used.

Alkali chlorides, alkali sulfates, ammonium sulfate, preferably sodium chloride, sodium sulfate, ammonium sulfate used.

Additions are e.g. Urea, alginate.

Alkali hydroxide, alkali carbonates, alkali hydrogen carbonates, Alkali hydrogen phosphates and their mixtures preferably: NaOH, KOH, sodium carbonate, potassium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, disodium hydrogen phosphate, Dipotassium hydrogen phosphate, trisodium phosphate, Tripotassium phosphate, mixtures of NaOH and Sodium carbonate or from KOH and potassium carbonate, especially preferred: sodium carbonate, mixtures of NaOH and sodium carbonate used.

The components mentioned are preferably in the following Quantity ratios used:

CD concentration in the liquor (weight percent) 0.5-70%, preferably 3-50%, particularly preferably 5-30%.

Salt concentration in the liquor (weight percent) 0-30%, preferably 0-20%, particularly preferably 0-10%.

Additional concentration in the liquor (weight percent) 0-30%, particularly preferably 0-20%.

Base concentration in the fleet (weight percent) 0.2-20% particularly preferably 0.5-10%.

Alkaline reinforcement in the fleet when using carbonates as base (weight percent caustic soda) 0.1-3%, especially preferably 0.3-1%.

To the textile materials or leather is described by the Cyclodextrin process preferably covalently in bound to the outside areas. So the cavities are the Cyclodextrins available and consequently all CD-typical applications possible.

• es können Wirkstoffe in das Cyclodextrin eingeschlossen und kontrolliert wieder abgegeben werden.
  Das Cyclodextrin wirkt hier wie ein Haftvermittler. Beispiele für solche Wirkstoffe sind: Biozide, Bakterizide, Insektizide, Fungizide, antimikrobielle Verbindungen (z.B. für die Verwendung in der Hospitalhygiene, Schuhausrüstung etc.), Herbizide, Pheromone, Duftstoffe (z.B. zur Duftausrüstung von Textilien), Geschmacksstoffe, pharmazeutische Wirkstoffe (z.B. für die Ausrüstung von Pflastern, Verbänden, Geweben für medizinische Anwendungen etc.), Wirkstoffe zur Antistatikausrüstung oder Flammschutzausrüstung, Stabilisatoren (z.B. gegen UV-Strahlung), Filter (z.B. gegen UV-Strahlung), Farbstoffe.
• Wirkstoffe können durch den Einschluß stabilisiert werden (gegen Licht, Temperatur, Oxidation, Hydrolyse, Verdampfung) und kontrolliert freigesetzt werden.

The cavity of the cyclodextrin can be used in a variety of ways. Some applications for finishing textile materials or leather may be mentioned as examples:

• Active ingredients can be included in the cyclodextrin and released again in a controlled manner.
  The cyclodextrin acts like an adhesion promoter here. Examples of such active ingredients are: biocides, bactericides, insecticides, fungicides, antimicrobial compounds (e.g. for use in hospital hygiene, shoe equipment etc.), herbicides, pheromones, fragrances (e.g. for scenting textiles), flavorings, pharmaceutical active ingredients (e.g. for the equipment of plasters, bandages, tissues for medical applications etc.), active ingredients for antistatic or flame retardant equipment, stabilizers (e.g. against UV radiation), filters (e.g. against UV radiation), dyes.
• Active ingredients can be stabilized by the inclusion (against light, temperature, oxidation, hydrolysis, evaporation) and released in a controlled manner.

Due to the possibility of cyclodextrins poorly water-soluble Complexing substances also results in completely new ones Properties of the materials.

This is how the storage of welding or welding breakdown products becomes into the textile material by complexing it Fabrics prevented. It is also easy to clean the corresponding materials connected (exchange of Sweat products against the surfactants in the wash solution). To there is no smell of sweat left on the material after washing back.

By complexing sweat or sweat breakdown products becomes the smell when wearing these textile materials significantly reduced.

In the case of mixed fibers, finishing with cyclodextrin derivatives the hydrophilicity and wettability of the fibers and thus increasing the comfort.

The described cyclodextrin derivatives according to the invention can be used as Starch substitute e.g. used for permanent crease resistance become.

The cyclodextrin derivative bound to textile material or leather can also be used as an adhesion promoter e.g. for polymeric fabrics with lipophilic residues. Leave with it textile materials or leather with completely new types Equip fabrics comfortably.

By reaction with cellulose, cellulose derivatives, polymers Sugars or their derivatives, gelatin, polyvinyl alcohols or PVA derivatives or polyallylamines Manufacture membranes, foils, films, etc. These are for Extraction purposes, e.g. Ultrafiltration, reverse osmosis, Dialysis, etc. particularly suitable.

By reaction with the cyclodextrin derivatives according to the invention known chromatography materials modify in their properties. For example the selectivity of these materials can be strong increase. Chromatography materials suitable for modification are, for example, silica gel, agarose, cellulose, Dextran, silica, diatomaceous earth-crosslinked cellulose or Diatomaceous earth agarose matrices.

The cyclodextrin derivatives according to the invention are suitable also for all for cyclodextrins and cyclodextrin derivatives known applications. Examples are mentioned the solubilization of water-insoluble or poorly soluble Substances in the pharmaceutical sector, for example, for increasing the bioavailability of a drug in food technology e.g. to stabilize antioxidants, in the cosmetics sector, e.g. to stabilize volatile substances or in the agro sector e.g. for the formulation of active ingredients as well as the known applications in process engineering (e.g. separations).

Cyclodextrin-containing polymers according to the invention are suitable especially for applications in chromatography or for Separations.

The following examples serve to further explain the Invention.

Laufmittel: Acetonitril/n-Butanol/konz. Ammoniak/Wasser = 5/2/1/4.

DC-Platten: Kieselgel, Fa. Merck Art. Nr. 802815.

¹H-bzw. ¹³C-NMRThe following methods were used to characterize the cyclodextrin derivatives:
Thin layer chromatogram (DC):

Eluent: acetonitrile / n-butanol / conc. Ammonia / water = 5/2/1/4.

TLC plates: silica gel, Merck Art. No. 802815.

¹ H or. ¹³ C NMR

The DS _Cl value for the nitrogen-containing heterocyclic radicals in the cyclodextrin derivatives of the examples was as follows:

To 1 g of the inventive cyclodextrin derivative to be investigated (correspondingly for samples with a high salt content 4.5 ml of water, 4.5 ml of diethylamine and 4.5 ml Given water. The solution was at room temp. touched and then i. Vac. evaporated, again with water added and evaporated to dryness again. After that was the residue in 20 ml dist. Water added, 2 d against least Water dialyzed (benzoylated cellulose: Sigma Art. No .: D 7884) and evaporated to dryness again. Possibly. existing Precipitate is filtered off. It does not contain Cyclodextrin.

The average degree of substitution (DS _Cl ) per anhydroglucose of active chlorine can then be determined by ¹ H-NMR (d6-DMSO / trifluoroacetic acid). It results from the following formula: DS Cl = (1/6 * I1) / ((I2 - 2/3 * I1) / 7) mean:

I1 = integral of the methyl protons of diethylamine from 0.5 - 1.75 ppm, I2 = total integral of all protons of anhydroglucose of the cyclodextrin derivative and the methylene protons of Diethylamine from 2.75 - 6 ppm.

The determination of the DS values for the others may still be in the Residues present derivatives were carried out as known from the prior art.

IR-Spektroskopie

Messung des Ausbleichens einer alkalischen Phenolphthaleinlösung (1N NaOH)
   Messung: DC-Scan in Reflexion bei 572 nm

The following methods were also used to characterize the cyclodextrin polymers:

IR spectroscopy

Measurement of the bleaching of an alkaline phenolphthalein solution (1N NaOH)
Measurement: DC scan in reflection at 572 nm

Dispersions were in a double-walled 2 liter reaction vessel made with anchor stirrer. The monomers and auxiliaries were added using fine dosing vessels. The catalysts e.g. (APS / Brüggolit) were classified as 4% and 2% Solutions metered in with the peristaltic pump. The temperature was done with the help of a thermostat and an internal temperature controller e.g. kept constant at 45 ° C.

The dispersions prepared in this way were Residual monomer content, viscosity, K value and particle size characterized. Wet residue and dispersion stability were judged.

To assess the film properties of those in the examples Dispersions prepared were the dispersions in a Poured the mold and then dried. It resulted a film with a film thickness of approx. 1 mm. The firmness Stickiness, sweating, appearance and hardness of the Films were assessed visually.

Example 1: Preparation of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin (sodium salt) DS _Cl 0.3 by reacting β-cyclodextrin with cyanuric chloride

10 g of water and 10 g of ice were mixed with 1.2 g of NaOH in a round bottom flask submitted. Within 30 min. were under vigorous Stir at a temperature of 0 to 5 ° C 5.5 g of cyanuric chloride added in three equal portions. At pH 7 and a temperature of 0-15 ° C was then a solution of 10 g β-cyclodextrin (10% water content), in 10 ml water and 1.2 g NaOH slowly and with vigorous stirring to the suspension dripped. After stirring for 1.5 h, the pH became 7 reached. The still cold suspension was removed using a The frit is suctioned off and the precipitate is discarded. After freeze drying of the filtrate, 13.8 g of chlorotriazinyl-β-cyclodextrin were obtained with an ash content of 25.5%.

The average degree of substitution of active chlorine was DS _Cl = 0.3. The water solubility was over 50% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 2: Preparation of 2-chloro-4-hydroxy-β-cyclodextrin (sodium salt) DS _Cl = 0.4

300 g of water, 0.6 g of Texapon K 12 and 150 g of ice were placed in a 2 l round bottom flask. Thereafter, 118.8 g of cyanuric chloride were added in one portion at 0 ° C. and the mixture was evacuated three times with stirring and vented again. 25.95 g of sodium hydroxide solution, dissolved in 270 g of water, were then added dropwise over the course of 1 hour. The temperature then rose to 3 ° C. The pH of the solution was above pH = 12 at this point. The stirring was continued until the pH had dropped to pH 7-8. Then it was given within 10 min. 5.19 g of sodium hydroxide solution dissolved in 150 g of water. The pH was then at pH = 11. The addition of 108 g of β-cyclodextrin (10% water content), dissolved in 270 g of water with 25.95 g of sodium hydroxide solution, was then started immediately at 0-5 ° C. The addition took 1 hour. The pH was then> 12. The mixture was stirred until the pH had dropped to pH = 11 and then adjusted to pH = 8-8.5 with approximately 20 ml of 0.8% phosphoric acid and suctioned off at 0-5 ° C. via a frit. The precipitate was discarded, the filtrate freeze-dried. The desired cyclodextrin derivative with DS _Cl = 0.4 and an ash content of 32% was thus obtained.

Example 3: Preparation of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin (sodium salt) DS _Cl 0.9

39.6 g of cyanuric chloride were placed under vigorous stirring in 150 g of water at 2 ° C. Then 8.65 g of NaOH in 28 g of water were added within 15 minutes. at 2-3 ° C internal temp. dripped. After the end of dosing, the pH of the suspension was pH = 10-11. 36 g of β-cyclodextrin (10% water content) - dissolved in 54 g of water with 8.65 g of NaOH - were then added within 40 min. added at 5-7 ° C. After the addition, the mixture was stirred at 7 ° C. for a further 25 min, the pH slowly falling to pH = 9-10. After filtration through a glass frit, the powdery precipitate was discarded and the filtrate, which had a pH = 7, was freeze-dried. This gave 67 g of the triazinyl-β-cyclodextrin derivative with 32% ash content (g / g) and a DS _Cl value of 0.9.

Example 4: Preparation of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin (sodium salt) DS _Cl 1.5 by reacting β-cyclodextrin with cyanuric chloride

20 g of water and 20 g of ice were initially charged with 3.6 g of NaOH. Then within 45 min. at T = 0 - 5 ° C, 16.5 g of cyanuric chloride are added in four portions. At pH = 7, 10 g of β-cyclodextrin (90%) dissolved in 30 ml of water with 3.6 g of NaOH were then slowly added dropwise to the suspension at T = 0-15 ° C. After 2 h a pH = 7 was reached. The still cold suspension was suction filtered and the precipitate was discarded. After freeze-drying the filtrate, 17.54 g of chlorotriazinyl-β-cyclodextrin with a salt content of 44% were obtained. The average degree of substitution of active chlorine was DS _Cl = 1.5. The water solubility was over 25% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 5: Preparation of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin, (Na salt) DS _Cl 0.5 by reacting β-cyclodextrin with cyanuric chloride

In a 63 liter kettle with an enamel coating, 10 kg of water were cooled to 1 ° C. and 8.6 kg of ice were added. After adding 10 g of sodium dodecyl sulfate as an emulsifier, 2 kg of cyanuric chloride were added to the well-stirred solution. A solution of 0.868 kg of sodium hydroxide in 4 kg of water was then added dropwise at a temperature of 0-5 ° C. in the course of 5 h. The pH should be below pH = 12 during this time. After the alkali had been added, the reaction solution was stirred at 5 ° C. for a further 0.5 h. This gave a clear solution of the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine in water. A mixture of 3.08 kg of β-cyclodextrin, 0.434 kg of sodium hydroxide and 4 kg of water was then added dropwise to this well-stirred solution at 5-15 ° C. in the course of 2 hours. During this addition, the pH should be between pH = 10 and pH = 13. The mixture was stirred for a further 1-2 hours until there was no more change in pH. The pH was then 9.6. The solution came to room temperature. It was then filtered through a 0.45 / 0.2 µm filter. After spray-drying the solution (inlet temperature = 235 ° C., outlet temperature = 120 ° C.), 5.4 kg of the triazinyl-β-cyclodextrin derivative with an ash content of 22% were obtained. The average degree of substitution of active chlorine was DS _Cl = 0.52. The water solubility was over 55% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 6: Preparation of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin, (Na salt) DS _Cl 0.5 by reacting β-cyclodextrin with the sodium salt of 2,4-dichloro-6-hydroxy1 , 3,5-triazine

25 kg of the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine as an 8% solution in water were added to a 63 liter kettle with an enamel coating, and the mixture was stirred at 10 ° C. cooled down. A (cooled) solution of 3 kg of β-cyclodextrin and 0.426 kg of sodium hydroxide in 4 kg of water was then added dropwise to the well-stirred solution over the course of 2 hours at 10-15 ° C. The pH was pH 10-13 during the dropping. After the addition of the β-CD solution, the reaction mixture was stirred without cooling for a further 2 hours until there was no more change in pH. The solution came to room temperature. The solution was then filtered through a 0.45 / 0.2 µm filter. After spray-drying the solution (inlet temperature = 235 ° C., outlet temperature = 120 ° C.), 5.5 kg of the triazinyl-β-cyclodextrin derivative with an ash content of 22% were obtained. The average degree of substitution of active chlorine was DS _Cl = 0.5. The water solubility was over 55% (g / g). No more β-cyclodextrin was detectable in the thin layer chromatogram.

Example 7: 2-chloro-4-hydroxy-triazinyl-γ-cyclodextrin (sodium salt) DS _Cl 0.9 by reacting γ-cyclodextrin with cyanuric chloride

20 g of water and 10 g of ice were initially charged with 2.4 g of NaOH. Then within 30 min. at T = 0 - 5 ° C 11 g of cyanuric chloride are added in three portions and the mixture is stirred at 5 ° C until a pH = 7 has been reached. 1.2 g of NaOH were added to the suspension. Then 10 g of γ-cyclodextrin (dissolved in 20 ml of water with 1.2 g of NaOH) were slowly added to the suspension at T = 0-15 ° C. After 1.5 h a pH = 7 was reached. The still cold suspension was suction filtered and the precipitate was discarded. After freeze-drying the filtrate, 20.9 g of chlorotriazinyl-γ-cyclodextrin with an ash content of 33% (g / g) were obtained. The average degree of substitution of active chlorine was DS _Cl = 0.9, the water solubility was 25% (g / g). Γ-Cyclodextrin was no longer detectable in the thin layer chromatogram.

Example 8: Chlorotriazinyl-β-Hydoxypropylcyclodextrin MS (hydroxypropyl) 0.77, DS _Cl 0.7 by reacting hydroxypropyl-β-cyclodextrin with cyanuric chloride

20 g of water and 10 g of ice were initially charged with 2.4 g of NaOH. Then within 30 min. at T = 0 - 5 ° C 11 g of cyanuric chloride added in four portions. At pH = 7, 10 g of HP-β-cyclodextrin MS 0.77 dissolved in 20 ml of water with 2.4 g of NaOH were then slowly added dropwise to the suspension at T = 0-15 ° C. After 1.5 h a pH = 7 was reached. The still cold suspension was suction filtered and the precipitate was discarded. After filtration and freeze-drying of the filtrate, 21.4 g of the chlorotriazinyl-β-hydroxypropyl-cyclodextrin derivative were obtained. The solubility in water was 25% (g / g), the ash content was 33% (g / g). The average active chlorine content per anhydroglucose unit was DS _Cl = 0.7.

Example 9: Preparation of dichlorotriazinyl-β-cyclodextrin DS _Cl 1.0 by reacting β-cyclodextrin with cyanuric chloride

9.1 g of β-cyclodextrin and 2 g of NaOH were placed in 26 g of water. 7.36 g of cyanuric chloride were added in 3 portions at 2 ° C. within 30 minutes and the mixture was stirred. After 2 h the pH was 7.2. The pH was stabilized by adding 4 g of Na ₂ HPO ₄ and 6 g of KH ₂ PO ₄ in 50 g of water. The solution was filtered cold and then freeze-dried. 19.6 g of the dichlorotriazinyl-cyclodextrin derivative with 39% ash content were obtained. The DS _Cl of active chlorine was 1.0.

Example 10: Reaction of 3-N-ethylamino-2-hydroxypropyl-β-cyclodextrin (MS 0.17) with cyanuric chloride (attachment of the Cyclodextrins to the heterocycle via a spacer)

3-N-ethylamino-2-hydroxypropyl-β-cyclodextrin (MS 0.17) was using the method of A. Deratani and B. Pöpping (Makromol. Chem., Rap. Commun. 13, 237-41 (1992)) by implementation of 3-chloro-2-hydroxypropyl-β-cyclodextrin with ethylamine manufactured.

1.1 g of cyanuric chloride were placed in 5 g of water, 5 g of ice and 0.24 g of NaOH at a temperature of 0 to 5 ° C. The suspension was stirred until a pH of pH = 7 was reached. Thereafter, 1 g of the basic β-cyclodextrin derivative (3-N-ethylamino-2-hydroxypropyl-β-cyclodextrin (MS 0.17)) dissolved in 5 g of water was added dropwise. The mixture was stirred at T <5 ° C for 5 hours. By adding 4 ml of 10% NaHCO ₃ solution (g / g), the pH was adjusted to 6.9 and the suspension was filtered. Freeze drying gave 1.6 g of the desired cyclodextrin derivative with a salt content of 42% (g / g). The average active chlorine content per anhydroglucose was DS _Cl = 0.1.

Example 11: Reaction of hydroxypropyl-β-cyclodextrin (MS 0.9) with 2,4,5,6-tetrachloropyrimidine

12 g of hydroxypropyl-β-cyclodextrin (MS 0.9) were dissolved in 30 g of water. 8.72 g of 2,4,5,6-tetrachloropyrimidine, dissolved in 30 ml of acetone, were then added dropwise with vigorous stirring at 30-35 ° C. and a pH of pH = 6-6.5 within 1 h. The pH was kept constant with an aqueous sodium hydroxide solution. After addition of the pyrimidine, stirring was continued for 1 h, the acetone was evaporated off, filtered and the filtrate was freeze-dried. 5 g of the reactive component according to the invention with a salt content of 31% and an active chlorine content of DS _Cl = 0.5 were obtained.

Example 12: Preparation of basic cyclodextrin derivatives by reacting monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (Example 2) with diethylamine

1.6 g of the monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4 (Example 2) were dissolved in 10 ml of water and mixed with 5 ml of diethylamine, 20 h at room temperature. stirred and then i. Vac. evaporated, mixed with water again and again evaporated to dryness. Then the residue was distilled in dist. Water added and 2 d against dist. Dialyzed water. The precipitate formed was filtered off (according to ¹³ C-NMR it contains no cyclodextrin). The solution was then evaporated to dryness. 1.6 g of the basic cyclodextrin derivative were thus obtained.

Example 13: Preparation of basic cyclodextrin derivatives by reacting monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with ethylamine

The reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (Example 2) with ethylamine was carried out as described in Example 10. 0.8 g of the amine derivative was obtained from 1 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4.

Example 14: Preparation of dihydroxy-triazinyl-β-cyclodextrin

15 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (Example 2) were heated to 70 ° C. in 1 l of water. The pH value dropped to pH = 3.9. Within 1 h, the solution was mixed with 3.3 g of NaOH - dissolved in 22 ml of water - and kept at 70 ° C. for two more hours. The pH was then adjusted to 7 with 2N HCl. The solution was then concentrated to 80 ml on a rotary evaporator.

This solution was then used over a period of 60 min. dropped in 720 ml of methanol. The precipitation was with Washed 90% methanol. 7.5 g of dihydroxy-triazinyl-β-cyclodextrin were obtained with a sodium chloride content of 5.8%.

Example 15: Reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with triethylamine to produce charged cyclodextrin derivatives

15 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 prepared according to Example 2 were dissolved in 60 ml of water and mixed with 30 ml of triethylamine. The clear solution was stirred at 60 ° C. for 24 h. For working up, the mixture was evaporated in vacuo, the residue in dist. Water absorbed and against dist. Dialyzed water 2 d. After freeze-drying, 19 g of the loaded cyclodextrin derivative were obtained. The average degree of substitution of triethylamine per anhydroglucose was 0.3. This derivative can also be used as a reactive component with triethylamine as a leaving group.

Example 16: Preparation of a water-insoluble cyclodextrin oligomer by reacting monochlorotriazinyl-β-cyclodextrin with yourself

7.5 g of monochlorotriazinyl-β-cyclodextrin prepared according to Example 2 was mixed with 2.5 g of sodium carbonate, in a grater well mixed and overnight at 80 ° C stored. There was an insoluble cyclodextrin polymer which is powdered in a mortar, thoroughly stirred in 1 l of water and was sucked off over a frit. 4.5 g were thus obtained of the insoluble cyclodextrin polymer.

Example 17: Preparation of a modified with cyclodextrin Polyallylamins by reacting monochlorotriazinyl-β-cyclodextrin with polyallylamine

5 g of polyallylamine (PAA, commercially available, for example, from Aldrich, Steinheim, under order number 28.321-5) were dissolved in 25 g of water. The pH of the solution was adjusted to pH = 7 with NaOH. The solution was mixed with 0.1 g Na ₂ CO ₃ and heated to 40 ° C. This was followed by the addition of 1.7 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) prepared analogously to Example 2. The solution obtained was heated to 98 ° C. in 45 min and mixed with a further 0.3 g of Na ₂ CO _{3 was} added and kept at this temperature for one hour. The pH was then 6.6. A blank with β-cyclodextrin instead of the triazinyl derivative was used as comparison. Here the pH at the end of the reaction was pH = 9.7. For working up, the mixture was adjusted to pH 7 with NaOH and 5 d against dist. Water dialyzed (dialysis tubing available, for example, from Sigma, Deisenhofen, under the order number Sigma D 9652) and then freeze-dried. The incorporation of the triazinyl derivative was demonstrated on the basis of the IR spectrum (KBr pellet). An insoluble polymer was formed from the soluble PAA.

Example 18: Illustration of a modified with cyclodextrin Polyvinyl alcohol by reacting monochlorotriazinyl-β-cyclodextrin with polyvinyl alcohol

The reaction was carried out as described in Example 17, but with polyvinyl alcohol (available, for example, from Wacker-Chemie, Munich under the name Wacker V03 / 180) as a soluble polymer. The pH was 7.7 at the end of the reaction. A soluble polymer was obtained. The incorporation of the triazinyl derivative was demonstrated by ¹³ C-NMR.

Example 19: Illustration of a modified with cyclodextrin Starch by reacting monochlorotriazinyl-β-cyclodextrin with strength

5 g of starch (available, for example, from Merck under item number Merck 1252.0250) were dissolved in water at 98 ° C. and cooled. At 40 ° C., 0.1 g of Na ₂ CO ₃ and 1.7 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) were added, prepared analogously to Example 2. Within 45 minutes. was heated to 98 ° C. The solution was then mixed with 0.3 g of Na ₂ CO ₃ and kept at 98 ° C. for 1 h.

A solid with a rubber-like consistency was formed. To Addition of 25 ml of water and cooling to room temperature was obtained one rubbery crumbs, which separated and 5 d against least Water were dialyzed (Sigma D 9652). The installation of the triazine derivative could be detected by an IR spectrum become. The product obtained was water-insoluble Polymer.

Example 20: Preparation of a modified with cyclodextrin Cellulose

1.7 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) prepared analogously to Example 2 were added to 25 g of water, 0.1 g of Na ₂ CO _{3 was} added to the solution and the mixture was stirred briefly at 40 ° C. . This was followed by the addition of 5 g of cellulose (available, for example, from Fluka under order number 22183). Within 45 min. the solution was heated to 98 ° C, after 15 min. or 30 min. 0.5 g of sodium chloride were added in each case. At 98 ° C, 0.3 g of Na ₂ CO _{3 was added} . The solution was kept at 98 ° C for 1 h. The mixture was then cooled to room temperature, the modified cellulose was filtered off with suction and washed thoroughly with water. The cellulose was then 5d against dist. Water dialyzed (Sigma D 9652). The incorporation of the triazinyl derivative was demonstrated on the basis of the IR spectrum. A cellulose treated in boiling water for 2 hours and a cellulose treated as described above but without the addition of the triazinyl derivative served as a comparison.

Example 21: Reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with cotton

Monochlorotriazinyl-β-cyclodextrins can be as follows described easily with common soda at 90-98 ° C Dyeing techniques of reactive monochlorotriazine dyes apply to cotton. The cotton (Style 407 and 467) was obtained from Testfabrics, Inc. (P.O. Box 420/200, Blackford Avenue, Middlesex, N.J. 08846-0420, USA).

20 g of cotton were prepared in a solution of 8 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) analogous to Example 2 and 0.5 g of soda were immersed in 100 ml of water and within 45 min. heated to 98 ° C. It was given after 15 min. each 2.5 g of sodium chloride to the solution. A further 1.5 g of soda were added at 98.degree. It was fixed at this temperature for 1 h. The fabric was removed from the bath and washed thoroughly with water. By measuring the bleaching of an alkaline phenolphthalein solution, it was shown that cyclodextrin was covalently bound to the cotton.
Cyclodextrin decolorizes alkaline phenolphthalein solution (see, for example, J. Chem. Soc. Perkin Trans. 2 1992). The coating of the cotton with cyclodextrin can therefore be determined by bleaching an alkaline phenolphthalein solution (solution in 1 N NaOH). The quantification was carried out by means of a DC scanner at 572 nm in the reflection position (instrument: Desaga, chromatogram densitometer CD 50) after the dye had been applied to the treated cotton in different concentrations. The untreated cotton and cotton, which had been treated analogously to the procedure described above, but with β-cyclodextrin instead of the triazinyl derivative, served as a comparison.

Example 22: Reaction of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 with filter paper

Several filter papers (30 x 10 cm) were prepared with a solution of 2.6 g of monochlorotriazinyl-β-cyclodextrin DS _Cl 0.4 (40% ash) analogously to Example 2 and 0.63 g of sodium carbonate in 50 ml of water and soaked at 80 ° C dried in a drying cabinet overnight. The papers were then washed 3 times with 1.5 l of water for 3 h each. As a comparison, another filter paper was soaked with the above solution without a triazine derivative and treated identically.

The paper coated with the cyclodextrin derivative was much smoother and firmer than the untreated one. The Treated papers decolorized alkaline phenolphthalein solution much stronger than the untreated. That at the So surface bound cyclodextrin derivative was still in able to complex phenolphthalein.

Example 23: Storage stability of monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4

5 g of the monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4 (Example 2) were in 50 ml 0.25 M phosphate buffer with different pH values, in dist. Water as well as in dist. Water, which had been adjusted to pH = 1 or pH = 14 with 2N HCL or 2N NaOH, dissolved. The pH of the solutions and the DS _Cl value of the cyclodextrin derivative were determined over 46 days.

Result:

The 2-chloro-4-hydroxy-1,3,5-triazinyl-β-cyclodextrin (sodium salt) is particularly stable in buffered solutions at pH = 8. pH values time water water water buffer buffer buffer buffer [d] pH = 1 pH = 14 pH = 5 pH = 6 pH = 7 pH = 8.5 0 pH = 7 pH = 1 pH = 14 pH = 5.2 pH = 6.2 pH = 7.1 pH = 8.5 3rd pH = 3.6 pH = 4.6 pH = 6.2 pH = 7.2 pH = 8.3 4th pH = 2.88 pH = 4.4 pH = 6.2 pH = 7.18 pH = 8 5 pH = -0.24 pH = 1 pH = 4.3 pH = 6.19 pH = 7.16 pH = 7.6 10 pH = -0.27 pH = 1.5 pH = 6.1 pH = 7.12 pH = 7.6 17th pH = -0.26 pH = 14 pH = 1.2 pH = 5.97 pH = 7.04 pH = 7.5 26 pH = 1.4 pH = 5.9 pH = 7 pH = 7.3 46 pH = -0.35 pH = 1.2 pH = 5.35 pH = 6.66 pH = 7 DS _Cl values time water water water buffer buffer buffer buffer [d] pH = 1 pH = 14 pH = 5 pH = 6 pH = 7 pH = 8.5 0 0.4 0.4 0.4 0.4 0.4 0.4 0.4 3rd 0.34 5 0.21 0 0.4 0.4 10 0.01 0.05 17th 0 0 0.37 26 0 0.3 0.33 46 0.35

Example 24: Dialysis of monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4

2 g of the monochlorotriazinyl-β-cyclodextrin DS _Cl = 0.4 (Example 2) were distilled in 10 ml. Dissolved water and 5 times against 10 l of dist. Water which had previously been adjusted to pH = 8.5 with 2N NaOH was dialyzed. The salinity then dropped to <0.5% (g / g). The DS _Cl value after dialysis was DS _Cl = 0.35.

Example 25: Determination of the incorporation rate of the triazine heterocycle in β-cyclodextrin in the production of 2-chloro-4-hydroxy-triazinyl-β-cyclodextrin, (Na salt) DS _Cl 0.5 by reacting β-cyclodextrin with the Sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine

785 g of the sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine as an 8% solution in water were placed in a 1 liter round-bottomed flask and cooled to 10 ° C. with stirring. A (cooled) solution of 135.76 g of β-cyclodextrin (dry weight) and 13.4 g of sodium hydroxide in 130 g of water was then added dropwise to the well-stirred solution within 1.5 h at 10-15 ° C. This resulted in a theoretical DS _Cl value of DS _Cl 0.4. The pH was pH 10-13 during the dropping. After the addition of the β-CD solution, the reaction mixture was stirred for a further 4 hours without cooling until there was no more pH change. A sample of this reaction mixture was then mixed with diethylamine to determine the DS _Cl value. In this test it was DS _Cl 0.35. This corresponds to an incorporation of the triazine heterocycle in β-cyclodextrin of 87.5%.

Analogously, further experiments were carried out to determine the installation rates for derivatives with different theoretical DS _Cl values. The following table provides information about the results. DS _Cl (theory) DS _Cl (product) Installation [%] 0.4 0.35 87.50 0.6 0.49 81.67 0.8 0.64 80.00 1 0.77 77.00

Example 26 (comparative example) Emulsion polymerization without MCT-β-CD

In a glass reactor, 349 g of demineralized water, 5.12 g 20% aqueous solution of the sodium salt of dihexyl sulfosuccinate and 6 g of 10% acetic acid. The pH the template was adjusted to 4.0 with 10% sodium hydroxide solution. 41 g of styrene and butyl acrylate were added with stirring emulsified and heated to 50 ° C. In a dosing container 320 g of water, 55.6 g of 30% sodium lauryl polyglycol sulfate, 81.9 g of acrylamide, 369 g of styrene and 369 g pre-emulsified butyl acrylate. The pH of the pre-emulsion was adjusted to pH 4.0 with 10% acetic acid. Subsequently metering was started simultaneously with stirring of solutions of 12.9 g of 40% tert-butyl hydroperoxide in 159 g water and 8.82 g hydroxymethanesulfinic acid in 163 g of water. After the start of the reaction, the pre-emulsion dosed evenly over 4 hours. After the pre-emulsion process has ended you metered the initiator system long until the solid content of the dispersion no longer rise. The pH value remained at pH = 4 held. It was then cooled. For complete polymerization were now 5.3 ml of 10% aqueous tert-butyl hydroperoxide solution and 4.3 ml of 10% aqueous hydroxymethanesulfinic acid solution admitted.

The result was a styrene-butyl acrylate copolymer with one Styrene content of 48.5% (w / w), a butyl acrylate content of 48.5% (w / w) and 3% acrylamide. The dispersion contained no coarse fraction, and had a fixed salary of 49% (w / w), a pH of 3.5 and an average particle size of 210 nm.

Example 27 Emulsion polymerization in the presence of MCT-β-CD

In a glass reactor, 349 g of demineralized water, 5.12 g 20% aqueous solution of the sodium salt of dihexyl sulfosuccinate and 6 g 10% acetic acid and 30 g MCT-β-CD (0.4) submitted in 30 ml of water. The pH of the template was adjusted to 4.0 with 10% sodium hydroxide solution. Under 41 g of styrene and butyl acrylate were each emulsified in with stirring and heated to 50 ° C. In a dosing container 320 g water, 55.6 g 30% sodium lauryl polyglycol sulfate, 81.9 g of acrylamide, 369 g of styrene and 369 g of butyl acrylate pre-emulsified. The pH of the pre-emulsion was 10% Acetic acid adjusted to pH 4.0. Then you started with stirring simultaneously with the addition of solutions of 12.9 g of 40% tert-butyl hydroperoxide in 159 g of water and 8.82 g hydroxymethanesulfinic acid in 163 g water. To At the start of the reaction, the pre-emulsion became uniform over 4 hours added. By simultaneously dosing sodium hydroxide solution the pH of the reaction mixture was kept at pH = 4.0. After the pre-emulsion process was complete, this was dosed Initiator system until the fixed content of the Dispersion no longer increased. The pH continued to rise kept at pH = 4. It was then cooled. For complete polymerization were now 5.3 ml 10% aqueous tert-butyl hydroperoxide solution and 4.3 ml 10% aqueous Hydroxymethanesulfinic acid solution added.

The result was a styrene-butyl acrylate copolymer with one Styrene content of 48.5% (w / w), a butyl acrylate content of 48.5% (w / w) and 3% acrylamide. The dispersion contained no coarse fraction, and had a fixed salary of 48.1% (w / w), a pH of 4.0 and an average particle size of 220 nm.

Example 28 Emulsion polymerization in the presence of MCT-β-CD

In a glass reactor, 349 g of demineralized water, 5.12 g 20% aqueous solution of the sodium salt of dihexyl sulfosuccinate and 6 g of 10% acetic acid. The pH the template was adjusted to 4.0 with 10% sodium hydroxide solution. 41 g of styrene and butyl acrylate were added with stirring emulsified and heated to 50 ° C. In a dosing container 320 g of water, 55.6 g of 30% sodium lauryl polyglycol sulfate, 81.9 g of acrylamide, 369 g of styrene and 369 g pre-emulsified butyl acrylate. The pH of the pre-emulsion was adjusted to pH 4.0 with 10% acetic acid. Subsequently metering was started simultaneously with stirring of solutions of 12.9 g of 40% tert-butyl hydroperoxide in 159 g water and 8.82 g hydroxymethanesulfinic acid in 163 g of water. After the start of the reaction, the pre-emulsion dosed evenly over 4 hours. After 75% of the pre-emulsion were metered in, a solution of 30 g was started MCT-β-CD (0.4) in 30 ml of water so that the dosage completed by pre-emulsion and MCT-β-CD (0.4) simultaneously were. The pH of the reaction mixture was simultaneous kept at pH = 4 by metering in 10N sodium hydroxide solution. After the pre-emulsion process was complete, this was dosed Initiator system until the fixed content of the Dispersion no longer increased. The pH continued to rise kept at pH = 4. It was then cooled. For complete polymerization were now 5.3 ml 10% aqueous tert-butyl hydroperoxide solution and 4.3 ml 10% aqueous Hydroxymethanesulfinic acid solution added.

The result was a styrene-butyl acrylate copolymer with one Styrene content of 48.5% (w / w), a butyl acrylate content of 48.5% (w / w) and 3% acrylamide. The dispersion contained no coarse fraction, and had a fixed salary of 48.8% (w / w), a pH of 3.9 and an average particle size of 260 nm.

Example 29 Emulsion polymerization in the presence of MCT-β-CD

In a glass reactor, 349 g of demineralized water, 5.12 g 20% aqueous solution of the sodium salt of dihexyl sulfosuccinate and 6 g of 10% acetic acid. The pH the template was adjusted to 4.0 with 10% sodium hydroxide solution. 41 g of styrene and butyl acrylate were added with stirring emulsified and heated to 50 ° C. In a dosing container 320 g of water, 55.6 g of 30% sodium lauryl polyglycol sulfate, 81.9 g of acrylamide, 369 g of styrene and 369 g pre-emulsified butyl acrylate. The pH of the pre-emulsion was adjusted to pH 4.0 with 10% acetic acid. Subsequently metering was started simultaneously with stirring of solutions of 12.9 g of 40% tert-butyl hydroperoxide in 159 g water and 8.82 g hydroxymethanesulfinic acid in 163 g of water. After the start of the reaction, the pre-emulsion dosed evenly over 4 hours. After the pre-emulsion process has ended you metered the initiator system long until the solid content of the dispersion no longer rise. Thereafter, a solution of 30 g of MCT-β-CD (0.4) in 30 ml of water are added and the pH is adjusted to 8 using 5 N sodium hydroxide solution posed. The reaction mixture was at 80 ° C / pH for 30 minutes = 8, the pH was left for a further 30 minutes drop to pH = 4. It was then cooled. For complete Polymerization was now 5.3 ml of 10% aqueous tert-butyl hydroperoxide solution and 4.3 ml 10% aqueous hydroxymethanesulfinic acid solution admitted.

The result was a styrene-butyl acrylate copolymer with a styrene content of 48.5% (w / w), a butyl acrylate content of 48.5% (w / w) and 3% acrylamide. The dispersion contained no coarse fraction and had a solids content of 49.5% (w / w), a pH of 4.0 and an average particle size of 350 nm. Composition of the polymer dispersions example Copolymer Comonomers MCT-β-CD (0.4) Tg [0 ° C] FG [%] pH Particle size nm 26 St / BA / AA 48.5 / 48.5 / 3 - 20th 49.0 3.5 210 27 St / BA / AA 48.5 / 48.5 / 3 30 g 20th 48.1 4.0 220 28 St / BA / AA 48.5 / 48.5 / 3 30 g 15 48.8 3.9 260 29 St / BA / AA 48.5 / 48.5 / 3 30 g 10 49.5 4.0 350

Example 30 Production of nylon modified with cyclodextrin

10 g nylon 6/6 (Fluka, CH-9471 Buchs, Order No. 74712) were finely ground, suspended in 40 ml of dimethylformamide. After adding 1.0 g of sodium carbonate and 5 g of MCT-β-CD (0.4), dissolved in 10 ml DMF was heated to 80 ° C and 1 h kept at this temperature. To work it up Filtered nylon granules, suspended in water and filtered. The incorporation of the triazine derivative was confirmed by 13 C NMR proven.

Example 31 Production of polyvinyl alcohol modified with cyclodextrin

10 g polyvinyl alcohol (Aldrich, Steinheim, Order No. 34, 158-4) were suspended in 20 ml of 10% sodium hydroxide solution, 1 Stirred for an hour and filtered. The resin was in one 10% solution of MCT-β-CD (DS 0.4) in water stirred for 15 minutes. It was then cooled and rinsed with water.

The polymer treated in this way showed complexing properties. For example, 1 g of the modified polyvinyl alcohol complexes 1.1 mg hydrocortisone from an aqueous hydrocortisone solution (Initial concentration 1.6 mg in 10 ml). The Polyvinyl alcohol used as the starting material showed no complex behavior.

Example 32 Production of polyvinyl alcohol modified with cyclodextrin

10 g polyvinyl alcohol (Aldrich, Steinheim, Order No. 34, 158-4) were suspended in 20 ml of 10% sodium hydroxide solution, 1 Stirred for an hour and filtered. The resin was in one 10% solution of MCT-β-CD (DS 0.8) in water stirred for 15 minutes. The resin was then filtered off and in Drying cabinet fixed at 80 ° C. It was then cooled and rinsed with water.

The polymer treated in this way showed complexing properties. For example, 1 g of the modified polyvinyl alcohol complexes 0.7 mg hydrocortisone from an aqueous hydrocortisone solution (Initial concentration 1.6 mg in 10 ml). The Polyvinyl alcohol used as the starting material showed no complex behavior.

Example 33 Production of polyvinyl alcohol modified with cyclodextrin

10 g polyvinyl alcohol (Aldrich, Steinheim, Order No. 34, 158-4) were suspended in 20 ml of 10% sodium hydroxide solution, 1 Stirred for an hour and filtered. The resin was in one 10% solution of MCT-γ-CD (DS 0.4) in water stirred for 15 minutes. The resin was then filtered off and in Drying cabinet fixed at 80 ° C. It was then cooled and rinsed with water.

The polyvinyl alcohol modified with MCT-γ-CD (DS 0.4) showed complexing properties. For example, complexed 1 g of the modified polyvinyl alcohol 1.4 mg hydrocortisone from an aqueous hydrocortisone solution (starting concentration 1.6 mg in 10 ml). The one as raw material Polyvinyl alcohol used showed no complexing behavior.

Example 34 Production of cyclodextrin modified polyethyleneimine

20 g of polyethyleneimine (50% aqueous solution, from Fluka, CH-9471 Buchs, order no. 03880), 10 g MCT-β-CD (0.4) and 2 g Sodium carbonate was heated to 98 ° C for 4 hours. The product had a gel-like consistency and discolored alkaline Phenolphthalein solution, what the complexing properties of the product (J. Chem. Soc. Perkin Trans. 2, 1992).

Example 35 Production of polymethacrylate modified with cyclodextrin

To dissolve 40 g of MCT-β-CD (0.4) in 60 ml of water, 10 ml of 2-hydroxyethyl methacrylate dissolved in 10 ml of water and 3.2 g Sodium hydroxide, dissolved in 10 ml of water, at the same time at 10 added dropwise to 20 ° C (duration 1 hour). The solution was dialyzed keeping the pH at 8 with a phosphate buffer has been.

In a cylindrical 1 liter glass vessel with an impeller stirrer and a heating jacket, 4.05 g of the emulsifier "Gafac RM 510" from GAF (Deutschland) GmbH, 5020 Frechen, (complex phosphoric acid ester) are added to N ₂ protective gas 405 ml of n-decane and stirred at 70 ° C and a stirrer speed of 750 rpm.

The solution prepared above was treated with 23 g of 5% (w / v) aqueous potassium peroxodisulfate solution added. This solution is poured into the n-decane phase with stirring. The resulting one Emulsion is stirred at 75 ° C and 750 rpm for 2.5 h, wherein pearl-shaped polymer is formed.

The suspension obtained is cooled to 25 ° C. and the polymer Solid is filtered off, with 100 ml of n-decane, 150 ml Ethanol, twice with 150 ml water and finally again washed with 150 ml of ethanol. The polymer is 6 h at 75 ° C. dried in vacuo.

42 g (yield: 90%) of polymer are obtained in the form of uniform beads with an average particle size of 25 μm . The polymer has a swelling of 1.9 g / g in water and a gel bed volume of 4.0 ml / g.

Example 36 Production of chitosan modified with cyclodextrin

10 g chitosan (low molecular weight, from Fluka, CH-9471 Buchs, Order no. 22741), 10 g MCT-β-CD (0.4) and 2 g sodium carbonate were heated to 98 ° C for 4 hours. The product had gel-like consistency and decolorized alkaline phenolphthalein solution, what the complexing properties of the Product documented (J. Chem. Soc. Perkin Trans. 2, 1992).

Example 37 Emulsion polymerization with MCT-β-CD

393 g of demineralized water, 6 g of a nonylphenol polyglycol ether (with an average of 23 EO units), 2.4 g of a C ₁₅ - were placed in a reactor which was provided with a reflux condenser, stirrer, metering options, nitrogen inlet and heating and cooling facilities. Alkyl sulfonates, 4.5 g of sodium vinyl sulfonate, 50 g of MCT-β-CD (DS 0.4), 4 g of acrylamide and 1.7 g of acrylic acid are introduced and the pH is adjusted to 3.5 with concentrated ammonia solution. 402 g of vinyl acetate, 170 g of vinyl laurate and 36 g of 2-ethylhexyl acrylate were emulsified into this solution. The mixture was heated to 50 ° C. and the metering in of a 3.5% ammonium persulfate solution (10.5 g / h) and a 2% sodium formaldehyde sulfoxylate solution (10.5 g / h) was started. After the start of the reaction, a mixture of 134 g of 2-ethylhexyl acrylate, 101 g of methyl methacrylate, 15 g of hydroxyethylate and 2.5 g of acrylic acid (dosage 1) and a solution of a further 6 g of the nonylphenol polyglycol ether and 18 g of N were added over a period of 4.5 hours -Methyloacrylamide in 36 g of demineralized water continuously metered. The dosing of the ammonium persulfate solution and the sodium formaldehyde sulfoxylate solution was then continued for 2.5 hours.

After cooling, a stable dispersion was obtained a fixed salary of 61.0%, a K value (according to Fikentscher, 1% in tetrahydrofuran / water 93: 7 (v / v)) of 101, as well as one Viscosity of 22,000 mPa.s (Brookfield, 20 rpm).

Example 38 (comparative example) Emulsion polymerization without using the MCT-β-CD

The experiment was carried out as in Example 37, where however, the addition of 50 g MCT-β-CD (DS 0.4) was omitted has been.

After cooling, a stable dispersion was obtained a fixed salary of 60.5%, a K-Wrt (according to Fikentscher, 1% in tetrahydrofuran / water 93: 7 (v / v)) of 11l, as well as one Viscosity of 19000 mPa.s (Brookfield, 20 rpm).

Example 39

The experiment was carried out as in Example 38 with the change that after 3.5 h of monomer addition Over 1 hour 30 g MCT-β-CD (DS 0.4) dissolved in 70 g demineralized Water can be dosed.

After cooling, a stable dispersion was obtained a fixed salary of 53%, a K value (according to Fikentscher, 1% in tetrahydrofuran / water 93: 7 (v / v) of 110, as well as one Viscosity of 15000 mPa.s (Brookfield, 20 rpm).

The application test of the dispersions from the Examples 37 to 39 as contact adhesive were carried out as follows:

Peeling stability (at 23 ° C and 50% relative humidity)

The example according aqueous contact adhesives and the dispersions of Comparative Examples cm ² beech rods dry on 20 x 2 in a layer thickness of 100 μ m wet, equivalent to 75 g / m ² was applied and 45 minutes under standard conditions (23 ° C, 50% relative humidity ) dried. A PVC strip with an area of 15.5 × 2 cm ^{2 was} then placed on the beech stick so that the adhesive coatings came into contact with one another and were then pressed with a 3.5 kg steel roller by rolling back and forth five times. The gluing was done so that the free end of the PVC strip protruded on a transverse side of the beech stick. A weight of 300 g was immediately attached to the free end of the PVC strip and the beech stick was fixed with the PVC strip on the underside in such a way that an angle of 90 ° was established between the glued and free end of the PVC strip. The attachment of the weight was designed so that the force was even across the entire width of the PVC strip. The time was determined in which the PVC strip peeled off under a constant load of 300 g over a distance of 10 cm. For this purpose, after a test period of one, three and seven days, the peeled section was measured and the quotient of the test time in minutes and peeling section in centimeters was formed. Table 7 shows the measured values of the peel strength after one, three and seven days. The values given are mean values from three individual measurements.

Shear resistance (at 23 ° C and 50% relative humidity)

The example according aqueous contact adhesives and the dispersions of Comparative Examples were produced from beech wood test specimens having dimensions of 7 x 2 x 0.5 cm in a layer thickness of 100 μ m wet applied and 20 minutes under standard air dried. Then two test specimens were put together in such a way that the adhesive coatings came into contact with one another and an overlapped adhesive area of 4 cm ^{2 was} formed. The specimens thus fixed were pressed together for 10 seconds with a pressure of 0.2 N / mm ² . The bonds produced in this way were stored under a standard climate for 24 hours. The test specimens were then attached vertically and loaded with a weight of 2 kg at an angle of 180 ° C. The time elapsed in minutes for the adhesive bond to break was recorded. Table 6 shows the measured values for the shear strength. The values given are mean values from three individual measurements.

Heat shear strength (as a function of temperature (T))

The aqueous contact adhesives according to the example and the dispersions of the comparative examples were applied to beechwood test specimens with dimensions of 7 × 2 × 0.5 cm in a layer thickness of 100 μm and dried for 20 minutes under a standard atmosphere. Then two test specimens were put together in such a way that the adhesive coatings came into contact with one another and an overlapped adhesive area of 4 cm ^{2 was} formed. The specimens thus fixed were pressed together for 10 seconds with a pressure of 0.2 N / mm ² . The bonds produced in this way were stored under a standard climate for 24 hours. The test specimens were then fastened vertically in a drying cabinet preheated to 50 ° C. and loaded with a weight of 2 kg at an angle of 180 °. The temperature of the drying cabinet was increased by 25 ° C. every 60 minutes. The temperature prevailing when the adhesive bond broke and the elapsed time in minutes were recorded. Table 6 shows the measured values for heat resistance. The values given are mean values from three individual measurements.

Tensile strength (at 23 ° C and 50% relative humidity)

The example according aqueous contact adhesives and the dispersions of Comparative Examples on beechwood test specimens with dimensions of 12.3 x 3 x 0.3 cm in a layer thickness of 100 μ m wet applied and 30 minutes under standard air dried. Then two test specimens were put together in such a way that the adhesive coatings came into contact with one another and an overlapped adhesive area of 9 cm ^{2 was} formed. The specimens thus fixed were pressed together for 10 seconds with a pressure of 0.8 N / mm ² . The tensile strength in N / mm ^{2 of} the test specimens produced in this way was determined immediately and after three days of storage in a standard atmosphere using a tensile testing machine (material testing machine 1445 from Zwick) at a speed of 50 mm / min. certainly. Table 5 shows the measured values for the tensile strengths after appropriate storage. The values given are mean values from six individual measurements each.

Peel strength (at 23 ° C and 50% relative humidity)

The recordable proper aqueous contact adhesives and the dispersions of Comparative Examples were applied to 20 x 2 cm ² large PVC strips (DIN-vinyl flooring), and to 15.5 x 2 cm ² large book rods in a layer thickness of 100 μ m wet, equivalent to 75 g / m ² dry, applied and dried for 45 minutes under a standard climate (23 ° C, 50% relative humidity). The PVC strip with an area of 155 × 2 cm ^{2 was} then placed on the beech stick in such a way that the adhesive coatings came into contact with one another and were then pressed with a 3.5 kg steel roller by rolling back and forth five times. The test specimens produced in this way were clamped in a tensile testing machine (material testing machine 1445 from Zwick) immediately or after 3 days of storage in a standard atmosphere and separated by pulling them off at an angle of 90 ° at a speed of 300 min / cm. The peel strength is the force to be applied in N / cm. Table 5 shows the measured values for the peel strength after appropriate storage. The values given are mean values from three individual measurements.

Results of the tests:

The dispersions according to Examples 37 u. 39 and the comparison dispersion 33 were tested according to the above methods. The results are described in Tables 5, 6 and 7

Example 40

An aqueous solution consisting of the following components is introduced into a pressure apparatus with a stirrer, jacket heating and metering pumps:
10700 g of water, 142 g of sodium acetate x 3 H ₂ O, 1760 g of a 20% strength by weight aqueous solution of nonylphenyl ethoxylated with 30 mol of ethylene oxide, 13700 g of a 5% strength by weight aqueous hydroxyethyl cellulose solution (HEC solution) (viscosity the 2% by weight aqueous solution 300 mPa.s), 572 g of a 30% by weight aqueous sodium vinyl sulfonate solution, 3.0 g of a 10% by weight aqueous iron ammonium sulfate solution and 150 g of MCT-β-CD. The pH of the solution is adjusted to 4 using 10% by weight acetic acid.

The apparatus is freed from atmospheric oxygen and it becomes Ethylene pressed into the apparatus. At 20 bar ethylene pressure 5900 g of vinyl acetate and 10% of a reducing agent solution dosed from 27.1 g of Rongalit in 2 l of water. It will heated to 60 ° C internal temperature and the ethylene pressure increased to 40 bar. Now 10% initiator solution 27.1 g of tert-butyl hydroperoxide are metered into 2000 g of water at an internal temperature of 60 ° C and it becomes a drain the heat of reaction cooled, 24600 g of vinyl acetate, the rest 90% of the reducing agent solution and the remaining 90% the initiator solution are then metered in, the Ethylene pressure is kept at 40 bar. After that, a solution metered in from 3432 g of sodium persulfate in 300 g of water and the inside temperature increased to 80 ° C and at 1 hour kept at this temperature. Then with stirring most of the unreacted ethylene outgassed and in collected in a gasometer and 2 l of water are added. Then apply vacuum within 2 h 2.6 l of water distilled off, reducing the residual vinyl acetate content the dispersion to 0.05% by weight, based on the dispersion, is reduced. By repeating the separation process a residual vinyl acetate content of 0.012% by weight is reached.

Characterization of the resulting copolymer dispersion

Solids content (% by weight) 55 pH value (electrode measurement) 4.5 Viscosity (mPa.s) 1500 Minimum film formation temperature (MFT) ° C <0 K-value (Fikentscher) 80

Example 41

Dispersionsdaten:

Feststoffgehalt (Gew.-%) 53 sonst wie bei Beispiel 40

The experiment was carried out as in Example 40, with the change that 150 g of MCT-β-CD in 350 g of water were metered in 1 hour before the end of the vinyl acetate metering, and no MCT-β-CD was introduced for this purpose.

Dispersion data:

Solids content (% by weight) 53 otherwise as in Example 40

Example 42 (comparative example)

The experiment was carried out as in Example 40 only without MCT-β-CD.

Dispersion data as in example 40 only viscosity (mPa.s) = 500.

Application test of Examples 40 to 42 as Binder for the production of interior paints:

General formulation of the highly filled interior paints produced for comparative tests Parts by weight water 3110 Methylhydroxyethylcellulose (2% aqueous solution visc. 3000 mPa.s) 60 Na salt of a polyacrylic acid of MG 2000 (30% by weight aqueous solution) 35 Sodium polyphosphate (10% by weight aqueous solution) 150 Sodium hydroxide solution (10% by weight solution) 20th Preservative 15 Defoamer 20th talc 600 kaolin 400 Titanium dioxide 700 Calcium carbonate (particle size 90% by weight <2 µm) 2300 Calcium carbonate (particle size 50% by weight <2 µm) 1500 Plastic dispersion (55% by weight) 1090 Total amount of emulsion paint 10,000

Production of interior dispersion paints according to the above Frame formulation

The powdery methylhydroxyethyl cellulose is in the Sprinkled in water and dissolved with stirring, then the Solutions of the Na salts of polyacrylic acid and polyphosphoric acid and the 10% by weight sodium hydroxide solution was added with stirring. The resulting viscous solution becomes the preservative and added the defoamer. With stirring a dissolver are first at a stirring speed from 2000 rpm. Titanium dioxide and the calcium carbonate types admitted. It will continue for 20 minutes at 5000 rpm. dispersed, where the temperature of the pigment / filler paste rises to 60 ° C. It is allowed to cool to 30 ° C. The pH is 9.3.

In order to investigate the parameters of the plastic copolymer dispersions described, 891 g of the pigment / filler paste are mixed with 109 g of the 55% by weight plastic copolymer dispersion to be tested in each case (3 min. Lenard stirrer at 1500 rpm). After one day the emulsion paints thus prepared were applied with a 300 μ m -Rakel on Leneta sheet, the coatings after 5 days of drying at 23 ° C and 50% rel. Humidity brushed off with the Gardner device and the number of double brush strokes (DBS) according to Gardner determined, which the coating can withstand. Increasing DBS numbers mean increasing paint quality. The results can be seen in Table 8.

Application examples for use as additives to hydraulic Binders.

Application studies:

In the attempts to determine bending, compression and A tensile strength according to DIN 1164 was used. In all tests, a plastic / cement value was used of K / Z = 0.15 (K / Z = 0.15 means 15% by weight of dispersion powder worked on the amount of cement used).

Recipe for DIN mortar according to DIN 1164:

Portland cement PZ-35F 900g Standard sand (= 2 bags) 2700g Silicone defoamer S-860 (from Wacker-Chemie) 7.2 g water 225 g Dispersion from Examples 27-29 250 g

The powdered recipe components become one Dry mortar mixed. The dry mortar was first used Water (50% of the amount) pasted, then the dispersion stirred in and with the remaining water to the water / cement value (W / Z) of 0.40 (mortar without solid dispersion) set. For producing the comparison mortar from dispersion of example 26, the water / cement value had to Can be increased by 0.45 to obtain a workable mortar.

The examination of the raw mortar properties shows the strong water-saving or liquefying effect of the dispersions according to the invention. The results are summarized in Table 9. Raw mortar data Dispersion mortar from example CONCENTRATION CAMP Air content% Slump without shaking [cm] after shaking [cm] without dispersion 0.45 3.7 10.0 13.0 Example 26 0.45 4.2 10.0 16.5 27 0.40 3.7 12.5 18.0 28 0.40 4.3 15.0 21.0 29 0.40 4.0 13.0 19.0

Mortar prisms with the dimensions 160 x 40 x 40 mm ^{3 were manufactured in} accordance with DIN 1164 for testing bending tensile strength and compressive strength. The test specimens were stripped after 2 days. The formwork was covered during this time.
The results of the flexural tensile and compressive strength tests are summarized in Table 10. Strengths after 28 days of storage in a wet climate (23 ° C, 50% relative humidity) example Bending tensile strength (N / mm ² ) Compressive strength (N / mm ² ) without dispersion 7.88 ± 0.35 47.2 ± 2.2 26 8.92 ± 0.24 89.8 ± 1.0 27 11.95 ± 0.54 46.0 ± 1.0 28 13.60 ± 0.37 48.1 ± 1.1 29 12.97 ± 0.86 49.5 ± 1.3

To test the adhesive tensile strength, the mortar was applied with a trowel using a template with a 4 mm layer thickness to concrete path slabs (B 550, 40 x 40 cm ² ) stored in a standard climate (23 ° C, 50% relative humidity). The plates were stored in a standard climate. One day before the test date, 6 test specimens were drilled out per plate with a core drill and round pull-off staples (diameter 55 mm, thickness 10 mm) were glued on with a two-component adhesive. Was deducted with a trigger device with a load increase rate of 250 N / sec.

The results of the adhesive tensile strength are summarized in Table 11. Adhesive strength after 28 days of storage in a standard climate (23 ° C, 50% relative humidity). example Adhesive tensile strength (N / mm ² ) without dispersion 1.38 ± 0.11 26 1.81 ± 0.14 27 2.90 ± 0.16 28 3.45 ± 0.14 29 3.10 ± 0.15

Example 43

In a 16 l stirred autoclave, 5200 g of water, 97 g of Sodium salt of a sulfated nonylphenol polyglycol ether with about 25 glycol units, 48 g of an alkyl sulfonate approx. 15 carbon atoms, 21 g acrylamide, 70 g acrylic acid and 250 g MCT-β-CD (DS 0.4) and 2160 g of vinyl acetate and 840 g Emulsified vinyl laurate.

The mixture was heated to 50 ° C. and saturated with ethylene up to 60 bar. Polymerization started by simultaneous Dosage of 80 ml / h of 10% ammonium persulfate solution and 5% Na formaldehyde sulfoxylate solution and the polymerization continuation by simultaneously dosing 40 ml / h each of the two solutions. After the start was made (recognizable by a pressure increase of approx. 2 bar), a mixture of 2280 g vinyl acetate, 600 g vinyl laurate and 400 g 2-hydroxyethyl acrylate and a solution of 285 g of the above nonylphenol polyglycol ether sulfate, 120 g acrylic acid and 18 g concentrated Dosed ammonia solution in 530 g of water. To about 2 hours the ethylene pressure had dropped to 60 bar and further maintenance of this pressure had to be continued Ethylene to be replenished.

After dosing of the monomer mixture and emulsifier solution was the ethylene pressure for a further 1.5 h and the dosage of Maintain initiator solutions for another 6 h. The Ethylene pressure fell to 25 bar.

After cooling and relaxing, a dispersion resulted 56.6% solids content, a viscosity of 450 mPa.s (Epprecht Rheometer, STV, CIII), a K value of 84 (after Fikentscher, Cellulosechemie, Volume 13, 58, (1932); measured in 1% tetrahydrofuran solution) and an ethylene content of Solids content of 32%.

Example 44

The test was carried out as described in Example 43, but without MCT-β-CD in the template, but with Add 290 g of MCT-β-CD (DS 0.4) in a 30% aqueous solution Solution (% by weight) for 1 h as separate dosing with start of dosing after 7 h monomer dosing.

Dispersion data: 54.0% solids content, viscosity 630 m / Pa.s, K value: 91 and ethylene content: 31% Example 45

The test was carried out as described in Example 43, but without MCT-β-CD.

Dispersion data: 56.7% solids, viscosity 630 m Pa.s, K value: 94 and 30.5% ethylene content.

Test methods for the dispersions according to Examples 43 to 45

The results of the tests are shown in the table below of thermal peel strength, surface stickiness, Peel strength (adhesive strength) and shear strength of prepared with the dispersions of the invention pressure sensitive adhesive coatings indicated. With the expression "Adhesive strips" are strips of flexible, foil-like Backing material coated with a film of an inventive Understanding dispersion.

a) Wärmeschälstandfestigkeit: Ein 5 x 8 cm² großer Klebestreifen wurde mit einer Fläche von 5 x 5 cm² auf eine Kristallglasplatte aufgelegt und mit einer 2,2 kg schweren mit Silicongummi überzogenen Stahlwalze durch zweimaliges Hin- und Herrollen angepreßt. Das Aufkleben erfolgte so, daß das freie Ende des Klebstreifens an einer Längsseite der Glasplatte überstand. Man befestigte sofort ein Gewicht von 50 g am freien Ende des Klebstreifens und fixierte die Glasplatte mit dem aufgeklebten Klebestreifen auf der Unterseite in einem auf 50°C vorgewärmte Trockenschrank auf eine Weise, daß sich zwischen verklebtem und freiem Ende des Klebestreifens ein Winkel von 90°C einstellte. Die Befestigung des Gewichts war so ausgebildet, daß die Kraft gleichmäßig über die gesamte Breite des Klebestreifens wirkte. Man stellte die Zeit fest, in der der Klebestreifen bei 50°C unter der konstanten Belastung von 50 g auf einer Strecke von 1 cm abgeschält wurde. Dazu wurde nach einer angemessenen Prüfzeit die geschälte Strecke ausgemessen und der Quotient aus Prüfzeit in Minuten und Schälstrecke in Zentimeter gebildet. Die angegebenen Werte sind Mittelwerte aus jeweils drei Einzelmessungen.

b) Oberflächenklebrigkeit: Ein 20 cm langer und 2,5 cm breiter Klebestreifen (Trägermaterial: polymerweichmacherhaltiges PVC, 0,1 mm dick) wurde in Form einer "Schlaufe" senkrecht hängend mit der Klebstoffschicht nach außen in den oberen Backen einer Zugprüfmaschine eingespannt. Anschließend wurde die "Schlaufe" durch Zusammenfahren der beiden Backen der Zugprüfmaschine senkrecht mit einer Geschwindigkeit von 100 mm/Minute auf eine waagerecht befestigte, sorgfältig gereinigte Glasplatte ohne Druckanwendung in einer Länge von etwa 3 cm aufgelegt. Danach erfolgte sofort mit gleicher Geschwindigkeit der Abzug des Klebestreifens von der Glasoberfläche. Die höchste für das Abziehen der "Schlaufe" benötigte Kraft wird als Maß für die Oberflächenklebrigkeit hergenommen.Der angegebene Wert ist der Mittelwert aus fünf Einzelmessungen, wobei jedesmal ein frischer Klebestreifen und eine frische Glasoberfläche verwendet wurden.

c) Schälfestigkeit (Klebkraft): Ein 20 cm langer und 2,5 cm breiter Klebestreifen wurde von einem Ende ausgehend in einer Länge von ca. 12 cm auf eine sorgfältig gereinigte Kristallplatte blasenfrei ausgelegt.

The following determination methods were used:

a) Thermal peel strength: A 5 x 8 cm ² large adhesive strip with an area of 5 x 5 cm ^{2 was placed} on a crystal glass plate and pressed with a 2.2 kg heavy steel roller covered with silicone rubber by rolling back and forth twice. The adhesive was applied so that the free end of the adhesive strip protruded on one long side of the glass plate. A weight of 50 g was immediately attached to the free end of the adhesive strip and the glass plate with the adhesive adhesive strip on the underside was fixed in a drying cabinet preheated to 50 ° C. in such a way that there was an angle of 90 ° between the glued and free end of the adhesive strip C set. The weight was attached so that the force was even across the entire width of the tape. The time was determined in which the adhesive strip was peeled off at 50 ° C. under the constant load of 50 g over a distance of 1 cm. For this purpose, the peeled section was measured after an appropriate test time and the quotient of the test time in minutes and peeling section in centimeters was formed. The values given are mean values from three individual measurements.

b) Surface tackiness: A 20 cm long and 2.5 cm wide adhesive strip (carrier material: polymer plasticizer-containing PVC, 0.1 mm thick) was clamped vertically in the form of a "loop" with the adhesive layer hanging outwards in the upper jaws of a tensile testing machine. The "loop" was then placed vertically at a speed of 100 mm / minute on a horizontally fastened, carefully cleaned glass plate without applying pressure in a length of about 3 cm by moving the two jaws of the tensile testing machine together. The adhesive strip was then immediately removed from the glass surface at the same speed. The maximum force required to pull off the "loop" is taken as a measure of the surface stickiness. The value given is the average of five individual measurements, each time using a fresh adhesive strip and a fresh glass surface.

c) Peel strength (adhesive strength): A 20 cm long and 2.5 cm wide adhesive strip was laid out from one end with a length of approx. 12 cm on a carefully cleaned crystal plate without bubbles.

The adhesive strip was pressed on by rolling 5 times (back and forth) with a 2.2 kg steel roller covered with silicone rubber. After storage for 3 minutes or 24 hours in a climatic room at 23 ° C. and 50% relative humidity, the adhesive strip was peeled off at a speed of 300 mm / minute at a 180 ° angle over a length of 5 cm. The average force required for this was measured.
The values given are mean values from 5 individual measurements each.

For all measurements, the tested adhesive dispersions were applied to the carrier films with a doctor blade in such a thickness that a uniform polymer layer of 24 to 26 g / m ² remained after drying.

The glass surfaces used in the investigations were cleaned by mechanically removing visible soiling with the aid of water and, if appropriate, cleaning agents, and then storing them in an acetone bath. Before using the cleaned test surfaces, the plates were at least 48 hours in a standard climate of 23 ° C / 50% rel. Humidity stored.

Example 46 Equipping a cotton T-shirt with MCT-β-CD 0.5

35 g MCT-β-CD DS 0.438, 5 g sodium carbonate

14 g sodium chloride

700 g water

70 g of fabric

MCT-β-CD, sodium carbonate were dissolved in water and the shirt half immersed. Within 45 min Liquor heated to 98 ° C. After 15 minutes and 30 min 7 g of sodium chloride added. The temperature of 98 ° C was held for 1 h. The T-shirt was removed from the fleet taken, cooled and thoroughly rinsed with water several times and washed cold.

The T-shirt so equipped with MCT-β-CD was on the skin carried. On the one equipped with the cyclodextrin derivative There was significantly less sweat odor on the side of the T-shirt. The t-shirt was worn a total of 4 times at 40 ° C with a normal detergent in the washing machine washed and worn again. The ability of the material Binding sweat odor through complexation was even after the 4th wash cycle is still present. The cyclodextrin derivative consequently had to be covalently linked.

Example 47 Equipping a cotton T-shirt with MCT-β-CD 0.5

20 g MCT-β-CD DS 0.4

1 g sodium carbonate

4 g sodium chloride

200 g water

109 g of fabric

MCT-β-CD and sodium carbonate were dissolved in 200 ml of water. The damp, well wrung out cotton T-shirt was then half immersed in this solution. After it the T-shirt was soaked up with the fleet a plastic bag inserted and at 60 ° C for 4 h in the drying cabinet annealed. Then it became thorough several times washed hot and cold with water.

The t-shirt so equipped with MCT-β-CD was worn. On the side of the T-shirt equipped with the cyclodextrin derivative there was significantly less smell of sweat.

Example 48 Coating of cotton fabric with MCT-β-CD 0.4

1) 1.024 g of sodium carbonate was dissolved in 45 ml of water. After that a total of 5 g of MCT-β-CD 0.4 was added (anhydrous) and stir until a clear solution is obtained.

2) 1g of cotton fabric (Style 407, see Example 21) was then with constant stirring with the tweezers for 5 min dipped in this prepared solution.

3) Then the fabric was placed on a PVC board, approx. 50x35 cm, smoothed out and with a VA tube so long under rollers squeezed (the squeezed liquid was always with removed with a cloth) until the weight of the fabric becomes practical no longer changed. With 1g of used fabric and a 10% MCT solution was the weight of the damp material at about 1.5g.

4) Now the fabric was in the air circulation cabinet at 90 - 100 ° C for 60 min fixed.

5) This was followed by a washing process. In addition, the fabric fixed with MCT-β-CD for 3 min under running hot water and washed under running cold water for 2 min (in between repeatedly expressed).

6) The wet material was now in the Petri dish over one Plastic stoppers placed and at 90 ° C in the drying cabinet 60 min dried.

7) The dried fabric was weighed out. The weight gain was 33 mg.

8) Then with the dry, coated fabric the hydrocortisone test described in Example 29 was carried out.

Points 2-6 can be repeated any number of times to increase the occupancy of the substance with MCT-β-CD.

Example 49 Complexation of hydrocortisone by MCT-coated Cotton fabric

1) Für die Stammlösung wurden 500 ml VE-Wasser mit 200 mg Hydrocortison ca. 16 h in einer gut verschlossenen Flasche am Laborschüttler geschüttelt. Anschließend wurde der Ansatz erst durch ein Faltenfilter filtriert und danach durch ein Sterilfilter, um ungelöste Feinanteile abzutrennen.

2) Von dieser klaren Lösung wurden 450 ml in einen 500 ml Meßkolben abgefüllt und mit VE-Wasser bis zur Marke aufgefüllt (=Stammlösung).

3) Mit Hilfe der HPLC wurde der Gehalt an gelöstem Hydrocortison in dieser Stammlösung bestimmt. Er betrug 0,253 mg/ml.

A) Preparation of a hydrocortisone stock solution:

1) For the stock solution, 500 ml demineralized water with 200 mg hydrocortisone were shaken in a well-sealed bottle on a laboratory shaker for approx. 16 h. The mixture was then first filtered through a pleated filter and then through a sterile filter in order to separate undissolved fine particles.

2) 450 ml of this clear solution were poured into a 500 ml volumetric flask and made up to the mark with deionized water (= stock solution).

3) The content of dissolved hydrocortisone in this stock solution was determined by means of HPLC. It was 0.253 mg / ml.

1) 5 ml der Stammlösung mit 5x0,253 mg = 1,265 mg Hydrocortison und 5 ml VE-Wasser wurden in eine 30 ml Weithalsflasche mit einer Meßpipette pipettiert. 1,033 g mit MCT-β-CD beschichteter, trockener Stoff aus Beispiel 28 wurde gefaltet und mit einem Spatel so in die Lösung gedrückt, daß der Stoff gut durchtränkt wurde.

2) Anschließend wurde am Laborschüttler bei RT 18 h geschüttelt.

3) Die Flüssigkeit wurde über einen Trichter in einen 50 ml Meßkolben dekantiert, der Stoff vorsichtig mit der Pinzette in den Trichter gezogen und mit einem Pistill gut abgepreßt.

4) Der Stoff wurde anschließend in einem Becherglas gewaschen. Dazu wurde er mit der Pinzette in 5 ml VE-Wasser gedrückt anschließend für 5 min in ein Ultraschallbad gestellt.

5) Das Waschwasser wurde wiederum in den Meßkolben dekantiert, der Stoff vorsichtig aus dem Becherglas herausgezogen und mit dem Pistill in einem Trichter wiederum über dem Meßzylinder ausgepreßt.

6) Anschließend wurde der Meßkolben bis zur Marke mit VE-Wasser aufgefüllt.

7) Mit Hilfe der HPLC wurde der Gehalt an nicht komplexiertem Hydrocortison in der Lösung bestimmt.

8) Parallel dazu wurde 1 g eines unbeschichteten Stoffes als Kontrolle völlig gleich behandelt.

B) Complexing hydrocortisone with MCT-coated cotton fabric

1) 5 ml of the stock solution with 5x0.253 mg = 1.265 mg hydrocortisone and 5 ml deionized water were pipetted into a 30 ml wide-mouth bottle with a measuring pipette. 1.033 g of MCT-β-CD-coated, dry fabric from Example 28 was folded and pressed into the solution with a spatula in such a way that the fabric was thoroughly soaked.

2) The mixture was then shaken on a laboratory shaker at RT for 18 h.

3) The liquid was decanted into a 50 ml volumetric flask via a funnel, the material was carefully pulled into the funnel with tweezers and squeezed out well with a pestle.

4) The fabric was then washed in a beaker. For this he was pressed with tweezers in 5 ml of demineralized water and then placed in an ultrasonic bath for 5 min.

5) The washing water was again decanted into the volumetric flask, the substance carefully pulled out of the beaker and pressed out again with the pestle in a funnel above the measuring cylinder.

6) The volumetric flask was then filled to the mark with demineralized water.

7) The content of non-complexed hydrocortisone in the solution was determined using HPLC.

8) In parallel, 1 g of an uncoated substance was treated as the same control.

Result:

During the hydrocortisone content in the volumetric flask during the control test with untreated cotton fabric unchanged at 1.3 mg, it sank after immersing the treated substance to 0.77 mg. This showed that the cavity of the cyclodextrin even after binding to cotton was still available.

Example 50 Coating of cotton fabric with MCT-β-CD 0.4

1) 1 g of cotton fabric (Style 407, see Example 21) was analogous to Example 48 with MCT-β-CD 0.4 by immersion once occupied in 10% MCT-β-CD (1st occupancy). Then was the hydrocortisone test was carried out.

2) The fabric was washed in a washing machine in a 70 ° C Wash program with a common detergent and rinsed.

3) The hydrocortisone test was then carried out analogously Example 49 performed.

4) Points 2) and 3) were repeated again.

5) After the third wash, the cotton fabric was again analogous to point 1) with MCT-β-CD. Then were points 2), 3) and 4) are repeated.

6) Again after the third wash the cotton fabric load again with MCT-β-CD as described in point 1). Subsequently points 2), 3) and 4) were repeated.

7) In parallel, 1 g of an uncoated substance was used as Control treated the same.

The following table summarizes the results:

Result:

This experiment showed that the equipment the fabric with MCT-β-CD is washable and that covalently bound cyclodextrin again and again can be loaded onto a guest.

Example 51 Application of the Frescolat ML fragrance to a MCT-coated one Cotton fabric

1) 1 g of cotton fabric (Style 407, see Example 21) was coated with 5.5% MCT-β-CD. The substance became analogous to this Example 48 immersed in a 20% aqueous MCT-β-CD 0.4 solution, dehumidified, fixed, washed and dried.

2) The coated fabric was now in on a watch glass put an exicator. A crystallization dish was placed next to it with 10 ml water and a second watch glass with 250 mg Frescolat ML.

3) The desicator was closed and in for 16 h at 50 ° C put a drying cabinet.

4) Then the desicator was allowed to come to room temperature, took out the slightly damp cloth and dried it Room temperature.

5) The fabric was then baked at 100 ° C to to remove uncomplexed Frescolat ML.

Result:

6) Um den Gehalt an Frescolat ML quantitativ zu bestimmen, wurde der Stoff in einem Kolben mit 110 ml Wasser bedeckt und insgesamt 150 min einer flüssig/flüssig-Extraktion mit 50 ml Hexan unterworfen.

7) Die abgekühlte Hexan-Phase wurde in einen 100 ml Meßkolben überführt und bis zur Marke mit Hexan aufgefüllt. Anschließend erfolgte die Gehaltsbestimmung an Frescolat ML über Gaschromatographie.

The dry cotton fabric has no smell. However, if it is slightly moistened, the herbal, emphatically minty note of the Frescolate ML is clearly recognizable.

6) In order to quantitatively determine the content of Frescolat ML, the substance was covered with 110 ml of water in a flask and subjected to a liquid / liquid extraction with 50 ml of hexane for a total of 150 min.

7) The cooled hexane phase was transferred to a 100 ml volumetric flask and made up to the mark with hexane. The content of Frescolat ML was then determined using gas chromatography.

Result:

A total of 2.834 mg of Frescolat ML was complexed on the fabric.

Example 52 Application of the Frescolat ML fragrance to a MCT-coated one Cotton fabric

1) 1 g of cotton fabric (Style 407, see Example 21) was coated with 5.5% MCT-β-CD. The substance became analogous to this Example 48 immersed in a 20% aqueous MCT-β-CD 0.4 solution, dehumidified, fixed, washed and dried.

2) The coated fabric was now immersed in water and well pressed. The only slightly damp material was then placed in a desicator. In addition, one hired second watch glass with 250 mg Frescolat ML.

3) The desicator was closed and in for 16 h at 50 ° C put a drying cabinet.

4) Then the desicator was allowed to come to room temperature, took out the slightly damp cloth and dried it Room temperature.

5) The fabric was then baked at 100 ° C to to remove uncomplexed Frescolat ML.

Result:

6) Um den Gehalt an Frescolat ML quantitativ zu bestimmen, wurde der Stoff in einem Kolben mit 110 ml Wasser bedeckt und insgesamt 150 min einer flüssig/flüssig-Extraktion mit 50 ml Hexan für insgesamt 150 min unterworfen.

7) Die abgekühlte Hexan-Phase wurde in einen 100 ml Meßkolben überführt und bis zur Marke mit Hexan aufgefüllt. Anschließend erfolgte die Gehaltsbestimmung an Frescolat ML über Gaschromatographie.

The dry cotton fabric has no smell. However, if it is slightly moistened, the herbal, emphatically minty note of the Frescolate ML is clearly recognizable.

6) In order to quantitatively determine the content of Frescolat ML, the substance was covered with 110 ml of water in a flask and subjected to a liquid / liquid extraction with 50 ml of hexane for a total of 150 min for a total of 150 min.

7) The cooled hexane phase was transferred to a 100 ml volumetric flask and made up to the mark with hexane. The content of Frescolat ML was then determined using gas chromatography.

Result:

A total of 3.481 mg of Frescolate ML was complexed on the fabric.

Claims (9)

1. Cyclodextrin derivative, characterized in that they contain at least one nitrogen-containing heterocycle having at least one electrophilic centre, where the electrophilic centres are identical or different and are carbon atoms to which halogen, in particular F or Cl, or an ammonium substituent, in particular trialkylammonium, or a substituted or unsubstituted pyridinium substituent, is covalently bonded.
2. Cyclodextrin derivatives of the following formula I:

   

   where R is OH or OR¹ or R² and

   R¹ is a hydrophilic radical which can be identical or different and

   R² is a nitrogen-containing heterocycle which is either linked directly or via a spacer by means of an ether, thioether, ester or amine bond,

   where the spacer is an alkyl or hydroxyalkyl radical having 1-12 carbon atoms, which is bonded to the anhydroglucose via an ether, thioether, ester or amine bond and
   the nitrogen-containing heterocycle includes at least one halogen or one ammonium substituent and is present at least once per cyclodextrin and
   n is 6, 7 or 8.
3. Cyclodextrin derivatives according to Claim 2, characterized in that R¹ is identical or different and is methyl, ethyl, n- or i-propyl, n- or i-butyl, C₂-C₆-hydroxyalkyl such as hydroxyethyl, hydroxy-i-propyl, hydroxy-n-propyl, C₃-C₆-oligohydroxyalkyl such as dihydroxy-i-propyl, dihydroxy-n-propyl, C₁-C₄-carboxyalkyl (in the form of the free acid or as an alkali metal salt) such as, for example, carboxymethyl, carboxyethyl, carboxy-i-propyl, carboxy-n-propyl or an alkali metal salt of said carboxyalkyl substituents, acetyl, propionyl, butyryl, sulphate, C₁-C₄-sulphonylalkyl (in the form of the free acid or as an alkali metal salt), C₂-C₄-carboxyhydroxyalkyl (in the form of the free acid or as an alkali metal salt), C₂-C₄-sulphonylhydroxyalkyl (in the form of the free acid or as an alkali metal salt) and oxalyl, malonyl, succinyl, glutaryl or adipyl (in the form of the free acid or as an alkali metal salt) and

   R² is identical or different and
   is -R³ _m-(CHR⁴)_o-R⁵-R⁶, where

   R³ is identical or different and is O,

   

   S, NH, or NR⁷ and

   R⁷ is identical or different and is C₁-C₆-alkyl and

   R⁴ is identical or different and is H or OH and

   R⁵ is NH, NR⁷, S, O or

   

   particularly preferably O, and R⁶, if R⁵ is NH, NR⁷, S or O, is either

   

   where R⁸ and R⁹ are identical or different and are halogen, preferably Cl or F, or

   R⁸ is NR¹⁰R¹¹, OH, Oalkali metal, OR⁷, O(i-C₃H₆), OCH₂CH₂OCH₃ or SO₃H and

   R⁹ is halogen, in particular Cl or F, or an ammonium substituent, in particular trialkylammonium, or substituted or unsubstituted pyridinium substituents, such as e.g.

   

   and

   R¹⁰ is hydrogen or an aliphatic radical, preferably a C₁-C₄-alkyl radical which can be substituted by OCH₃, OC₂H₅, COOH, OSO₃H, SO₃H, OCH₂CH₂SO₂CH₂CH₂OSO₃H, OCH₂CH₂SO₂CH=CH₂, OCH₂CH₂SO₂CH₂CH₂Cl, SO₂CH₂CH₂OSO₃H, SO₂CH=CH₂, or a cycloaliphatic radical, preferably a 5- to 6-membered cycloalkyl radical, or araliphatic radical, preferably radicals of the formula

   

   where p = 1-4 and the radical A can be substituted, for example, by Cl, NO₂, COOH, SO₃H, CH₃, OCH₃, SO₂CH₂CH₂OSO₃H, SO₂CH=CH₂, CH₂SO₂CH₂CH₂OSO₃H, CH₂SO₂CH=CH₂, and

   R¹¹ has the meanings mentioned for R¹⁰ or is a phenyl radical or substituted phenyl radical, preferably a phenyl radical substituted by Cl, NO₂, COOH, SO₃H, CH₃, OCH₃, SO₂CH₂CH₂OSO₃H, SO₂CH=CH₂, CH₂SO₂CH₂CH₂OSO₃H, CH₂SO₂CH=CH₂
   or R⁶ is

   

   where

   R¹², R¹³ and R¹⁴ are identical or different and are halogen, preferably Cl or F,
   or R⁶, if R⁵ is

   

   is

   

   or

   

   and

   o is an integer from 0 to 12 and

   m is 0 or 1, where
   for o=0, m=0 also applies.
4. Cyclodextrin derivatives selected from the group 2,4-dichloro-1,3,5-triazinylcyclodextrins, 2-chloro-4-hydroxy-1,3,5-triazinylcyclodextrins (sodium salts), 2-fluoro-4-hydroxy-1,3,5-triazinylcyclodextrins (sodium salts), 2,4,5-trichloropyrimidylcyclodextrins, 5-chloro-2,4-difluoropyrimidylcyclodextrins, 6-(2,3-dichloro)-quinoxalinoylcyclodextrins, 5-(2,4-dichloro)pyrimidinoylcyclodextrins, 2-amino-4-chloro-1,3,5-triazinylcyclodextrins, 2-chloro-4-ethylamino-1,3,5-triazinylcyclodextrins, 2-chloro-4-diethylamino-1,3,5-triazinylcyclodextrins and 2-chloro-4-methoxy-1,3,5-triazinylcyclodextrins.
5. Process for the preparation of cyclodextrin derivatives according to one of Claims 1 to 4, characterized in that native α-, β- and/or γ-cyclodextrin and/or a suitable α-, β- and/or γ-cyclodextrin derivative is reacted in a suitable reaction medium in the presence of an acid acceptor and optionally of a surface-active ingredient in weakly acidic to strongly basic medium at temperatures from -10 to +70°C with suitable nitrogen-containing heterocycles and optionally subsequently worked up in an otherwise known manner in the neutral or weakly basic range, optionally with the aid of a buffer.
6. Solutions containing cyclodextrin derivatives according to one or more of Claims 1 to 4, characterized in that they have a pH from 7 to 9.
7. Compositions which contain cyclodextrin derivatives according to one or more of Claims 1 to 4 in bonded form.
8. Selective separating media for chromatography, characterized in that they contain cyclodextrin derivatives according to one or more of Claims 1 to 4 or compositions according Claim 7.
9. Membranes, foils, films, textiles or leathers to which cyclodextrin derivatives according to one or more of Claims 1 to 4 are covalently bonded.